JP2019044192A - Composition, liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

To provide a composition having good printability.SOLUTION: The composition contains: at least one polymer (A) selected from the group consisting of a polyamic acid, a polyimide, and a polyamic acid ester; and a solvent. The solvent contains at least one selected from the group consisting of a compound represented by formula (b1) and a compound represented by formula (b2). In the formulae, R is a C1-3 alkyl group; n is an integer of 0-2; and m is an integer of 0-2.SELECTED DRAWING: None

Description

  The present invention relates to a composition, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display device.

  Conventionally, a liquid crystal alignment film of a display element, a surface protective film for a display element or a lighting device, an interlayer insulating film, and the like are produced by applying a polymer composition on a substrate. For example, various liquid crystal display devices have been developed which have various driving methods in which the electrode structure and the physical properties of liquid crystal molecules to be used differ, and TN type, STN type, vertical alignment type (VA type), in-plane switching There are known various liquid crystal display devices such as a liquid crystal display (IPS type), an FFS type, and an optically compensated bent type (OCB type). These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of a liquid crystal aligning film, polyamic acid and a polyimide are generally used from the point which various characteristics, such as heat resistance, mechanical strength, and affinity with a liquid crystal, are favorable.

  In a polymer composition such as a liquid crystal alignment agent, a polymer component is dissolved in a solvent, and the liquid crystal alignment agent is applied to a substrate and heated to form a liquid crystal alignment film. Here, as a solvent for the liquid crystal aligning agent, for the purpose of dissolving the polymer uniformly, for example, aprotic polar solvents such as N-methyl-2-pyrrolidone and γ-butyrolactone are generally used. In addition, as a solvent for the liquid crystal aligning agent, usually, along with a good solvent such as these polyamic acids, for example, butyl cellosolve etc. in order to improve the coatability (printability) of the liquid crystal aligning agent when applying the liquid crystal aligning agent to the substrate. And a poor solvent having a relatively low surface tension (see, for example, Patent Document 1 and Patent Document 2).

  In recent years, liquid crystal display devices are used not only in conventional display terminals such as personal computers, but also in various applications such as liquid crystal televisions, car navigation systems, mobile phones, smartphones, and information displays. With such versatility, liquid crystal display devices are required to further improve display quality and improve product yield, etc. The improvement of the liquid crystal aligning film which is one of the structural members, and the liquid crystal aligning agent which is a formation material of the said liquid crystal aligning film is advanced. For example, in terms of display quality and yield, the liquid crystal aligning agent is required to have good coatability (printability) when applied on a substrate, and various materials for improving printability are required. It is proposed (for example, refer patent document 3 and patent document 4).

JP, 2010-97188, A JP, 2010-156934, A JP, 2011-257527, A JP 2011-257736 A

  The demand for higher performance and yield improvement of liquid crystal display elements is further increasing, and further improvement is also required for the printability of the liquid crystal aligning agent.

  This invention is made in view of the said subject, and the main purpose of providing the liquid crystal aligning film and liquid crystal display element which used the composition and liquid crystal aligning agent with favorable printability, and the said liquid crystal aligning agent. I assume.

  As a result of intensive studies to achieve the problems of the prior art as described above, the present inventors use a specific solvent as at least a part of the solvent component in a composition containing polyimide or its precursor as a polymer component. As a result, the inventors have found that the above-mentioned problems can be solved, and have completed the present invention. Specifically, the present invention provides the following composition, a liquid crystal aligning agent, a liquid crystal aligning film, and a liquid crystal display element.

  The present invention provides, in a first aspect, a composition comprising at least one polymer (A) selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and a solvent, wherein the solvent is There is provided a composition comprising at least one selected from the group consisting of a compound represented by the formula (b1) and a compound represented by the following formula (b2). Moreover, this invention is a liquid crystal aligning agent containing the said polymer (A) and a solvent in a 2nd side, Comprising: The compound by which the said solvent is represented with a following formula (b1), and a following formula (b2) The liquid crystal aligning agent containing at least 1 type chosen from the group which consists of a compound represented by these is provided.

（式（ｂ−１Ａ）中、Ｘ、Ｙは、それぞれ独立に−ＣＯＯ−又は−ＯＣＯ−であり、Ａ、Ｃ^１は、それぞれ独立に炭素数１〜６の１価の炭化水素基であり、Ｂは炭素数１〜１２の２価の炭化水素基である。）

（式（ｂ−１Ｂ）中、Ｒ^１、Ｒ^２は、それぞれ独立に炭素数３〜６のアルキル基であり、Ｒ^３はそれぞれ独立に水素原子又はメチル基であり、ｎ４は２又は３である。）

（式（ｂ１）中、Ｒは炭素数１〜３のアルキル基であり、ｎは０〜２の整数である。式（ｂ２）中、ｍは０〜２の整数である。）

(In the formula (b-1A), X and Y each independently represent -COO- or -OCO-, and A and C ¹ each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, And B are divalent hydrocarbon groups having 1 to 12 carbon atoms.)

(In formula (b-1B), R ¹ and R ² each independently represent an alkyl group having 3 to 6 carbon atoms, R ³ independently represents a hydrogen atom or a methyl group, and n ⁴ represents 2 or 3) is there.)

(In formula (b1), R is an alkyl group having 1 to 3 carbon atoms, and n is an integer of 0 to 2. In the formula (b2), m is an integer of 0 to 2).

  The composition and the liquid crystal aligning agent can be coated on a substrate by containing at least one selected from the group consisting of a compound represented by the above formula (b1) and a compound represented by the following formula (b2) as a solvent component (Printability) is good. Further, the composition of the present invention can be suitably used not only for liquid crystal alignment film applications but also for insulating films for display elements and lighting devices, and protective films.

  One aspect of the composition and the liquid crystal aligning agent is that the solvent contains a compound represented by the above formula (b-1A). Moreover, the other one aspect of a composition and a liquid crystal aligning agent is that the said solvent contains the compound represented by the said Formula (b-1B). In these cases, even when stored in a low temperature environment for a long time, precipitates are less likely to be generated in the composition or the orienting agent, and the storage stability is good. Moreover, the coating property with respect to the board | substrate of a composition or a liquid crystal aligning agent is also favorable. Furthermore, even if the liquid crystal display element is narrowed, a liquid crystal display element which exhibits excellent display quality can be obtained.

  In the composition and the liquid crystal aligning agent of the present invention, the solvent contains a compound represented by the above formula (b1) or (b2). In this case, the solubility of the polymer in the solvent is good. In addition, the compound represented by the above formula (b1) or (b2) has a moderately high boiling point, whereby the solvent volatilizes from the top of the printing press when the composition or the liquid crystal aligning agent is printed on the substrate Can be suppressed. Therefore, the polymer component does not easily precipitate on the printing press, and as a result, the printability (particularly, the printability when printing is continued for a long period of time, hereinafter also referred to as "long-term printability") is good. Can be

（式（ｄ−１）中、Ｘ^１及びＸ^２は、それぞれ独立に、単結合、−Ｏ−、−Ｓ−、−ＯＣＯ−又は−ＣＯＯ−であり、Ｙ^１は、酸素原子又は硫黄原子であり、Ｒ^１１及びＲ^１２は、それぞれ独立に、炭素数１〜３のアルカンジイル基であり、Ｒ^８及びＲ^９は、それぞれ独立に、水素原子又は保護基である。ｎ１は０又は１であり、ｎ２及びｎ３は、ｎ１＝０の場合、ｎ２＋ｎ３＝２を満たす整数であり、ｎ１＝１の場合、ｎ２＝ｎ３＝１である。式（ｄ−２）中、Ｘ^３は、単結合、−Ｏ−又は−Ｓ−であり、ｍ１は０〜３の整数である。ｍ２は、ｍ１＝０の場合に１〜１２の整数であり、ｍ１が１〜３の整数の場合にｍ２＝２である。式（ｄ−３）中、Ｒ^３は、炭素数１〜１２の１価の炭化水素基であり、Ｒ^４は、水素原子、又は炭素数１〜１２の１価の炭化水素基であり、Ｒ^５及びＲ^６は、それぞれ独立に、水素原子又はメチル基である。式（ｄ−４）中、Ｘ^４及びＸ^５は、それぞれ独立に、単結合、−Ｏ−、−ＣＯＯ−又は−ＯＣＯ−であり、Ｒ^７は、炭素数１〜３のアルカンジイル基であり、Ａ^４は、単結合又は炭素数１〜３のアルカンジイル基である。ａは０又は１であり、ｂは０〜２の整数であり、ｃは１〜２０の整数であり、ｋは０又は１である。但し、ａ及びｂが同時に０になることはない。式（ｄ−５）中、Ａ^５は単結合、炭素数１〜１２のアルカンジイル基又は炭素数１〜６のフルオロアルカンジイル基を示し、Ａ^６は−Ｏ−、−ＣＯＯ−、−ＯＣＯ−、−ＮＨＣＯ−、−ＣＯＮＨ−又は−ＣＯ−を示し、Ａ^７はステロイド骨格を有する１価の有機基を示す。） In the liquid crystal aligning agent of the present invention, the polymer (A) is derived from at least one diamine selected from the group consisting of compounds represented by the following formulas (d-1) to (d-5) It is preferable to include a polymer having a partial structure.

(In formula (d-1), X ¹ and X ² are each independently a single bond, -O-, -S-, -OCO- or -COO-, and Y ¹ is an oxygen atom or a sulfur atom R ¹¹ and R ¹² are each independently an alkanediyl group having 1 to 3 carbon atoms, R ⁸ and R ⁹ are each independently a hydrogen atom or a protecting group, n 1 is 0 or 1 N2 and n3 are integers satisfying n2 + n3 = 2 when n1 = 0, and n2 = n3 = 1 when n1 = 1, and in the formula (d-2), X ³ is a single integer. Is a bond, -O- or -S-, m1 is an integer of 0 to 3. m2 is an integer of 1 to 12 when m1 = 0, and m2 if m1 is an integer of 1 to 3 In the formula (d-3), R ³ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ⁴ is a hydrogen atom or carbon R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and in the formula (d-4), X ⁴ and X ⁵ are each independently And a single bond, -O-, -COO- or -OCO-, R ⁷ is an alkanediyl group having 1 to 3 carbon atoms, and A ⁴ is a single bond or an alkanediyl having 1 to 3 carbon atoms A is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, k is 0 or 1, provided that a and b are simultaneously 0. never in formula ^{(d-5), a} 5 represents a single bond, alkanediyl group or a fluoroalkyl alkanediyl group having 1 to 6 carbon atoms having 1 to 12 carbon atoms, ^{a 6} is -O -., - COO -, - OCO -, - NHCO -, - CONH- or -CO- indicates a monovalent organic ^{a 7} is having a steroid skeleton Are shown.)

  When at least a part of the polymer component of the liquid crystal aligning agent is the polymer (A) obtained by using the above-mentioned specific diamine, the above effect is high and suitable.

  In the liquid crystal aligning agent of the present invention, the molecule has one primary amino group in the molecule and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group is a chain hydrocarbon group or an alicyclic hydrocarbon group. The amine compound (C) to which it is bound may further be contained.

  In the liquid crystal aligning agent containing the above polymer (A) as at least a part of the polymer component, when the above amine compound (C) is contained as an additive, the liquid crystal aligning agent is stored under a low temperature environment for a long time At the same time, the above-mentioned amine compound (C) may be precipitated in the alignment agent. In this point, according to the liquid crystal aligning agent of the present configuration, the solvent component contains at least one selected from the group consisting of the compound represented by the above formula (b1) and the compound represented by the following formula (b2) Even when stored in a low temperature environment for a long time, precipitates are hardly generated in the alignment agent, and storage stability is good. In addition, the coatability of the liquid crystal aligning agent to the substrate is also good.

  The present invention provides, in a third aspect, a liquid crystal alignment film formed of the liquid crystal alignment agent of the present invention. Moreover, this invention provides the liquid crystal display element which comprises the said liquid crystal aligning film in a 4th side. Since the said liquid crystal aligning film is formed using the liquid crystal aligning agent with favorable printability, the yield of a liquid crystal display element can be raised.

The schematic block diagram of a FFS type liquid crystal cell. The top view schematic diagram of the top electrode used for manufacture of the liquid crystal display element by the optical orientation method. (A) is a top view of a top electrode, (b) is the elements on larger scale of a top electrode. The figure which shows four drive electrodes.

«Composition and liquid crystal aligning agent»
The composition and the liquid crystal aligning agent according to the present embodiment contain, as a polymer component, at least one polymer (A) selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and the polymer (A) Is prepared as a liquid composition which is dispersed or dissolved in a solvent. The composition according to the present embodiment is preferably a liquid crystal aligning agent.

«Polymer (A)»
<Polyamic acid>
The polyamic acid in the present embodiment can be obtained by reacting tetracarboxylic acid dianhydride with diamine.

（式（ｔ−１）中、Ｘ^７、Ｘ^８、Ｘ^９及びＸ^１０は、それぞれ独立に、単結合又はメチレン基であり、ｊは１〜３の整数である。）
で表される化合物などを；
芳香族テトラカルボン酸二無水物として、例えばピロメリット酸二無水物などを；それぞれ挙げることができるほか、特開２０１０−９７１８８号公報に記載のテトラカルボン酸二無水物を用いることができる。なお、テトラカルボン酸二無水物は、上記のものを１種単独で又は２種以上組み合わせて使用することができる。 [Tetracarboxylic acid dianhydride]
Examples of the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic acid dianhydride. Examples of these are
Examples of aliphatic tetracarboxylic acid dianhydrides include 1,2,3,4-butanetetracarboxylic acid dianhydride;
Examples of alicyclic tetracarboxylic acid dianhydrides include 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- Without 1,2-dicarboxylic acid Things, 3,5,6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10-Tetraone, cyclohexane tetracarboxylic acid dianhydride, the following formula (t-1)

(In formula (t-1), X ⁷ , X ⁸ , X ⁹ and X ¹⁰ are each independently a single bond or a methylene group, and j is an integer of 1 to 3).
Compounds and the like;
Examples of the aromatic tetracarboxylic acid dianhydride include, for example, pyromellitic acid dianhydride and the like, and besides, tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. The tetracarboxylic acid dianhydrides can be used singly or in combination of two or more.

  Here, examples of the compound represented by the above formula (t-1) include bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride, bicyclo [4.3. 0] Nonane-2,4,7,9-tetracarboxylic acid dianhydride, bicyclo [4.4.0] decane-2,4,7,9-tetracarboxylic acid dianhydride, bicyclo [4.4. 0] decane-2,4,8,10-tetracarboxylic acid dianhydride, tricyclo [6.3.0.0 <2,6>] undecane-3,5,9,11-tetracarboxylic acid dianhydride And the like. Among the compounds represented by the above formula (t-1), bicyclo [3.3.0] octane-2,4,6,8 from the viewpoint of enhancing the stability of liquid crystal alignment in liquid crystal alignment film applications. -Tetracarboxylic dianhydride is preferred.

  Among the above, as the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid, a compound represented by the above formula (t-1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2 It is preferable to use at least one compound selected from the group consisting of 3,4-cyclobutanetetracarboxylic acid dianhydride and pyromellitic acid dianhydride (hereinafter, also referred to as specific tetracarboxylic acid dianhydride). . When using said specific tetracarboxylic acid dianhydride, the usage-amount of the sum total of specific tetracarboxylic acid dianhydride is 10 mol% or more with respect to the total amount of tetracarboxylic acid dianhydride used for the synthesis of polyamic acid Is preferably 20 to 100 mol%. In addition, the polymer which has the partial structure originating in specific tetracarboxylic dianhydride is obtained by superposition | polymerization which contains specific tetracarboxylic dianhydride in a monomer composition.

[Diamine]
As a diamine used for the synthesis of the polyamic acid, a compound represented by the above formula (d-1), a compound represented by the above formula (d-2), a compound represented by the above formula (d-3), Containing at least one diamine selected from the group consisting of a compound represented by the above formula (d-4) and a compound represented by the above formula (d-5) (hereinafter, also referred to as “specific diamine”) Is preferred.

(Compound represented by formula (d-1))
In the above formula (d-1), examples of the alkanediyl group having 1 to 3 carbon atoms of R ¹¹ and R ¹² include, for example, methylene group, ethylene group, propane-1,2-diyl group, propane-1,3-diyl group Group, propane-2,3-diyl group and the like. Among these, preferred is a methylene group, an ethylene group or a propane-1,3-diyl group.
X ¹ and X ² are a single bond, -O-, -S-, -OCO- or -COO-. Note that X ¹ and X ² may be the same or different. Among these, a single bond, -O- or -S- is preferable.
Y ¹ is an oxygen atom or a sulfur atom. Preferably, it is an oxygen atom.
The protective group of R ⁸ and R ⁹ is preferably a group which is released by heat, and examples thereof include a carbamate-based protective group, an amide-based protective group, an imide-based protective group, and a sulfonamide-based protective group. As the protective group for R ⁸ and R ^9, a carbamate-based protective group is particularly preferable. Specific examples thereof include a tert-butoxycarbonyl group, a benzyloxycarbonyl group, a 1,1-dimethyl-2-haloethyloxycarbonyl group, 1 1,1-dimethyl-2-cyanoethyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, 2- (trimethylsilyl) ethoxycarbonyl group and the like. Among these, the tert-butoxycarbonyl group is particularly preferable in that it is highly removable by heat and in that the amount of remaining of the deprotected portion in the film can be reduced.

The two primary amino groups possessed by the compound represented by the formula (d-1) may be bonded to the same benzene ring when n1 = 0, or one bonded to two different benzene rings. It may be On the other hand, in the case of n1 = 1, two primary amino groups are bound to different benzene rings, one each.
The bonding position of the primary amino group on the benzene ring is not particularly limited. For example, when there is one primary amino group on the benzene ring, its bonding position may be any of 2-position, 3-position and 4-position with respect to other groups, in 3-position or 4-position. It is preferably present, and more preferred is 4-position. In addition, in the case where there are two primary amino groups on the benzene ring, the bonding position may be, for example, the 2,4-, 2,5- or the like position with respect to the other group, and in particular, the 2,4-position. Is preferred.
The hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or at least one hydrogen atom on the hydrocarbon group is substituted by a fluorine atom. It may be substituted by a group or a fluorine atom. Examples of the monovalent hydrocarbon group in this case include an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, and an aryl group having 5 to 10 carbon atoms A phenyl group, a tolyl group, etc., a C5-C10 aralkyl group (benzyl group etc.), etc. are mentioned.

  In the present specification, "hydrocarbon group" is meant to include a chain hydrocarbon group, an alicyclic hydrocarbon group and an aromatic hydrocarbon group. In addition, the “chain hydrocarbon group” means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed only of a chain structure. The chain structure may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. However, it does not need to be comprised only with the structure of alicyclic hydrocarbon, and the thing which has chain structure in the part is also included. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a chain structure or a structure of alicyclic hydrocarbon may be included in part thereof.

  As a preferable specific example of a compound represented by the said Formula (d-1), as a compound which is n1 = 0, a 4, 4'- diamino diphenylamine, a 2,4- diamino diphenylamine etc. are said; For example, it is n1 = 1 As compounds, for example, 1,3-bis (4-aminobenzyl) urea, 1,3-bis (4-aminophenethyl) urea, 1,3-bis (3-aminobenzyl) urea, 1- (4-aminobenzyl) ) -3- (4-Aminophenethyl) urea, 1,3-bis (2- (4-aminophenoxy) ethyl) urea, 1,3-bis (3- (4-aminophenoxy) propyl) urea, 1,3 3-bis (4-aminobenzyl) thiourea, 1,3-bis (2-aminobenzyl) urea, 1,3-bis (2-aminophenethyl) urea, 1,3-bis (2- (2- (2- (2-aminobenzyl) urea) Mino benzoyloxy) ethyl) urea, 1,3-bis (3- (2-amino-benzoyloxy) propyl) urea or the like; may be mentioned, respectively. In addition, as a compound represented by the said Formula (d-1), these compounds can be used individually by 1 type or in combination of 2 or more types.

(Compound represented by formula (d-2))
In the above formula (d-2), X ³ is a single bond, -O- or -S-, preferably a single bond or -O-.
When m1 = 0, m2 is an integer of 1-12. In this case, from the viewpoint of improving the heat resistance of the obtained polymer, m2 is preferably 1 to 10, and more preferably 1 to 8. Further, in the application of the liquid crystal alignment film, m1 = 0 is preferable from the viewpoint of improving the rubbing resistance while maintaining good liquid crystal alignment, and in the viewpoint of reducing the pretilt angle of liquid crystal molecules, m1 is 1 It is preferable that it is an integer of -3.
Although the bonding position of the primary amino group on the benzene ring is not particularly limited, it is preferable that each primary amino group be in the 3- or 4-position relative to the other group, and more preferably in the 4-position. . The hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or at least one hydrogen atom on the hydrocarbon group is substituted with a fluorine atom. It may be substituted by a valent group or a fluorine atom.

  Preferred specific examples of the compound represented by the above formula (d-2) include, for example, bis (4-aminophenoxy) methane, bis (4-aminophenoxy) ethane, bis (4-aminophenoxy) propane and bis (4). -Aminophenoxy) butane, bis (4-aminophenoxy) pentane, bis (4-aminophenoxy) hexane, bis (4-aminophenoxy) heptane, bis (4-aminophenoxy) octane, bis (4-aminophenoxy) nonane Bis (4-aminophenoxy) decane, bis (4-aminophenyl) methane, bis (4-aminophenyl) ethane, bis (4-aminophenyl) propane, bis (4-aminophenyl) butane, bis (4-aminophenyl) butane Aminophenyl) pentane, bis (4-aminophenyl) hexane, bis (4-aminophenyne) ) Heptane, bis (4-aminophenyl) octane, bis (4-aminophenyl) nonane, bis (4-aminophenyl) decane, 1,3-bis (4-aminophenylsulfanyl) propane, 1,4-bis ( 4-aminophenylsulfanyl) butane etc. can be mentioned. In addition, as a compound represented by the said Formula (d-2), the compound of these illustrations can be used individually by 1 type or in mixture of 2 or more types.

(Compound represented by formula (d-3))
In the above formula ^{(d-3), R} 3 is a monovalent hydrocarbon group having 1 to 12 carbon atoms. Specific examples of R ³ include, for example, alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and decyl group; And alkenyl groups such as allyl group; cycloalkyl groups such as cyclopentyl group and cyclohexyl group; aryl groups such as phenyl group and tolyl group; and aralkyl groups such as benzyl group. The carbon number of R ³ is preferably 1 to 6, and more preferably 1 to 3. R ³ is preferably a chain hydrocarbon group, more preferably a chain hydrocarbon group containing a carbon-carbon double bond, and still more preferably an alkenyl group.

R ⁴ is a hydrogen atom or a C 1-12 monovalent hydrocarbon group. As the said hydrocarbon group, a C1-C12 chain | strand-shaped hydrocarbon group, a C3-C12 alicyclic hydrocarbon group, a C5-C12 aromatic hydrocarbon group can be mentioned, As specific examples, groups exemplified in the description of R ³ above can be mentioned. As R ⁴ , a hydrogen atom or a chain hydrocarbon group having 1 to 12 carbon atoms is preferable. The hydrocarbon group in R ⁴ preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms.
R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, and preferably both are a hydrogen atom.

  In the diaminophenyl group of the above formula (d-3), the bonding position of the two primary amino groups is not particularly limited, but the 2,4-position or 2 relative to the group having an N-allyl structure bonded to a benzene ring The 5- and 5-positions are preferred, and the 2,4-position is more preferred. The hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or at least one hydrogen atom on the hydrocarbon group is substituted by a fluorine atom. Or a fluorine atom.

Preferred specific examples of the compound represented by the above formula (d-3) include, for example, 2,4-diamino-N, N-diallylaniline, 2,5-diamino-N, N-diallylaniline, a compound of the following formula (d The compound etc. which are represented by each of -3-1)-(d-3-3) can be mentioned. In addition, the compound represented by the said Formula (d-3) can be used individually by 1 type or in mixture of 2 or more types.

(Compound represented by formula (d-4))
In the formula (d-4), ^{"- X 4 - (R 7 -X} 5) k - " as the divalent group represented by the alkanediyl group having 1 to 3 carbon atoms, * - O -, * -COO- or _{* -O-C 2 H 4 -O-} ( where bond marked with "*" is bonded to the diamino phenyl group.) is preferably.
The group “—C _c H _{2 c + 1} ” is preferably linear, and specific examples thereof include methyl, ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl Group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl Groups, n-octadecyl group, n-nonadecyl group, n-eicosyl group etc. can be mentioned.
The two primary amino groups in the diaminophenyl group are preferably in the 2,4- or 3,5-position relative to the group "X ⁴ ", and more preferably in the 2,4-position. The hydrogen atom on the benzene ring to which the primary amino group is bonded is a monovalent hydrocarbon group having 1 to 10 carbon atoms, or at least one hydrogen atom on the hydrocarbon group is substituted by a fluorine atom. Or a fluorine atom.

Preferred specific examples of the compound represented by the above formula (d-4) include, for example, compounds represented by each of the following formulas (d-4-1) to (d-4-12) it can.

(Compound represented by formula (d-5))
In formula (d-5), A ⁵ represents a single bond, an alkanediyl group having 1 to 12 carbon atoms, or a fluoroalkanediyl group having 1 to 6 carbon atoms, and A ⁶ represents —O—, —COO—, or —OCO -, - NHCO -, - CONH- or -CO- indicates, ^{a 7} represents a monovalent organic group having a steroid skeleton.
The alkanediyl group having 1 to 12 carbon atoms in the ^{A 5} in the above formula (d-5), preferably alkanediyl group having 1 to 4 carbon atoms, a methylene group, an ethylene group, 1,3-propanediyl, 1 And 4-butanediyl are more preferred. As the fluoroalkanediyl group having 1 to 6 carbon atoms, a perfluoroalkanediyl group having 1 to 4 carbon atoms is preferable, and -CF _2- , perfluoroethylene group, 1,3-perfluoropropanediyl group, 1,4 Perfluorobutanediyl is more preferred.
As A ⁶ , -O- is preferable.
The steroid skeleton in the A ^7, Shikuropentano - perhydro phenanthridine consisting Ren core structure or a carbon - one or more than one carbon bond refers to a structure in which a double bond. As a monovalent organic group having such a steroid skeleton, those having 17 to 40 carbon atoms are preferable.

  Preferred specific examples of the compound represented by the above formula (d-5) include 1-cholesteryloxymethyl-2,4-diaminobenzene, from the viewpoint of giving a high pretilt angle to the coating film in the application of the liquid crystal alignment film. 1-Cholesteryloxymethyl-3,5-diaminobenzene, 1- (1-cholesteryloxy-1,1-difluoromethyl) -2,4-diaminobenzene, 1- (1-cholesteryloxy-1,1 -Difluoromethyl) -3,5-diaminobenzene, 1- (1-cholestanyloxy-1,1-difluoromethyl) -2,4-diaminobenzene, 1- (1-cholestanyloxy-1,1-difluoro Methyl) -3,5-diaminobenzene, 3- (2,4-diaminophenylmethoxy) -4,4-dimethylcholestane, 3- (1- (2,4-diaminophenyl)- 1,1-Difluoromethoxy) -4,4-dimethylcholestane, 3- (3,5-diaminophenylmethoxy) -4,4-dimethylcholestane, 3- (1- (3,5-diaminophenyl) -1 1,1-Difluoromethoxy) -4,4-dimethylcholestane, 3-((2,4-diaminophenyl) methoxy) cholan-24-acid hexadecyl, 3- (1- (2,4-diaminophenyl) -1 1,1-Difluoromethoxy) cholan-24-acid hexadecyl, 3-((3,5-diaminophenyl) methoxy) cholan-24-acid hexadecyl, 3- (1- (3,5-diaminophenyl) -1,1 -Difluoromethoxy) cholan-24-acid hexadecyl, 3- (2,4-diaminophenylmethoxy) cholan-24-acid stearyl, 3- (1- (2,4-di) Minophenyl) -1,1-difluoromethoxy) cholan-24-acid stearyl, 3- (3,5-diaminophenylmethoxy) cholan-24-acid stearyl, 3- (1- (3,5-diaminophenyl) -1 1,1-Difluoromethoxy) cholan-24-acid stearyl, 1-cholesteryloxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, 1-cholesperyloxy-2,4-diaminobenzene and 3, It is preferable to use one or more selected from the group consisting of cholestanyl 5-diaminobenzoate, and among these, in view of giving a high pretilt angle at a small usage rate, 1-cholesteryloxy-2,4-. Diaminobenzene, cholesteryl 3,5-diaminobenzoate, 1-cholestanyloxy-2,4-diaminobenzene It is particularly preferred to use at least one selected from the group consisting of Zen and 3,5-diaminobenzoic acid cholestanyl.

  In the synthesis of the polyamic acid, the specific diamine can be appropriately selected from the above compounds according to the drive mode of the liquid crystal display element to be produced. Specifically, a liquid crystal aligning agent suitable for FFS (Fringe Field Switching) type liquid crystal display devices can be manufactured by using the compound represented by the above formula (d-1) as the above specific diamine. . In addition, a TN (Twisted Nematic) type liquid crystal display can be obtained by using at least one selected from the group consisting of a compound represented by the above formula (d-2) and a compound represented by the above formula (d-3) A liquid crystal aligning agent suitable for devices can be produced, and at least one selected from the group consisting of a group represented by the above formula (d-4) and a compound represented by the above formula (d-5) is used By doing this, it is possible to manufacture a liquid crystal aligning agent suitable for vertical alignment type liquid crystal display elements.

(Other diamines)
As a diamine used for the synthesis of polyamic acid, compounds other than the above-mentioned specific diamines (other diamines) may be used. As the said other diamine, an aliphatic diamine, an alicyclic diamine, aromatic diamine, a diamino organosiloxane etc. can be mentioned, for example. As specific examples of these other diamines, as aliphatic diamines, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 1,3-bis (aminomethyl) cyclohexane Etc. as cycloaliphatic diamines, such as 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) etc.

As aromatic diamines, for example, p-phenylenediamine, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (triol) Fluoromethyl) -4,4'-diaminobiphenyl, 2,7-diaminofluorene, 4,4'-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '-(p -Phenylenediisopropylidene) bisaniline, 4,4 '-(m-phenylenediisopropylidene) bisaniline, 1,4-biphenyl (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N'-bis (4-amino Phenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl)- 2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1- (4-aminophenyl) -2,3-dihydro-1,3, -Trimethyl-1H-indene-6-amine, 4- (4'-trifluoromethoxybenzyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzyloxy) cyclohexyl-3, 5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) Cyclohexane, 4-aminobenzylamine, 3-aminobenzylamine, 2,2-bis [4- (4 Etc. aminophenoxy) phenyl] propane;
As a diamino organosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like can be mentioned, respectively, and diamine described in JP-A-2010-97188 can be used. In addition, these other diamines can be used individually by 1 type or in combination of 2 or more types.

  In the case where the polymer (A) contains a polymer having a partial structure derived from a specific diamine (hereinafter, also referred to as "specific polymer"), the content ratio of the specific polymer is a composition from the viewpoint of printability. The amount is preferably 50 parts by weight or more, more preferably 70 parts by weight or more, and preferably 80 parts by weight or more based on 100 parts by weight of the total amount of polymer components contained in the liquid crystal or liquid crystal aligning agent More preferably, it is particularly preferably 90 parts by weight or more.

（式（ｅ１−１）及び式（ｅ１−２）中、Ｒ^２０は、ハロゲン原子、炭素数１〜１０のアルキル基又は炭素数１〜１０のアルコキシ基であり、Ｚ^１は、単結合、酸素原子又は炭素数１〜３のアルカンジイル基である。ｒ２、ｒ５及びｒ６は、それぞれ独立に１又は２の整数であり、ｒ１、ｒ３及びｒ４は、それぞれ独立に０〜２の整数であり、ｒ７及びｒ８は、それぞれ独立に、ｒ７＋ｒ８＝２を満たす０〜２の整数である。但し、ｒ３＋ｒ５＋ｒ７≦５であり、ｒ４＋ｒ６＋ｒ８≦５である。式中、複数のＲ^２０が存在する場合、それらＲ^２０は独立して上記定義を有する。） In the case where the liquid crystal aligning agent according to the present embodiment contains a specific amine compound (C) described in detail below as an additive, the polymer (A) is a diamine having a carboxyl group (hereinafter, referred to as “carboxyl group-containing diamine It is preferable to include a polymer having a partial structure derived from “). Such a polymer can be obtained, for example, in the case of a polyamic acid, by using a carboxyl group-containing diamine as at least a part of the other diamine used in the synthesis of the polyamic acid. The carboxyl group-containing diamine is preferably an aromatic diamine, and specific examples thereof include compounds represented by the following formulas (e1-1) and (e1-2).

(In the formula (e1-1) and the formula (e1-2), R ²⁰ represents a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms, Z ¹ represents a single bond, An oxygen atom or an alkanediyl group having 1 to 3 carbon atoms, each of r2, r5 and r6 independently represents an integer of 1 or 2; r1, r3 and r4 each independently represents an integer of 0 to 2; , R7 and r8 are each independently an integer of 0 to 2 satisfying r7 + r8 = 2, provided that r3 + r5 + r7 ≦ 5 and r4 + r6 + r8 ≦ 5, wherein a plurality of R ^20, when present, R ²⁰ independently has the above definition.)

In Formula (e1-1) and Formula (e1-2), examples of the alkyl group having 1 to 10 carbon atoms for R ²⁰ include methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl groups. And octyl group, nonyl group, decyl group, etc., which may be linear or branched. As a C1-C10 alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, hexyloxy group etc. are mentioned, for example.
The alkanediyl group having 1 to 3 carbon atoms in Z ^1, may be, for example, a methylene group, an ethylene group, and trimethylene group.
r1, r3 and r4 are preferably 0 or 1, more preferably 0.

  Specific examples of the carboxyl group-containing diamine include, as a compound represented by the following formula (e1-1), for example, 3,5-diaminobenzoic acid, 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid and the like As a compound represented by the following formula (e1-2), for example, 4,4′-diaminobiphenyl-3,3′-dicarboxylic acid, 4,4′-diaminobiphenyl-2,2′-dicarboxylic acid, 3'-Diaminobiphenyl-4,4'-dicarboxylic acid, 3,3'-diaminobiphenyl-2,4'-dicarboxylic acid, 4,4'-diaminodiphenylmethane-3,3'-dicarboxylic acid, 4,4 ' -Diaminobiphenyl-3-carboxylic acid, 4,4'-diaminodiphenylmethane-3-carboxylic acid, 4,4'-diaminodiphenylethane-3,3'-dicarboxylic acid, 4,4 ' It can be mentioned; diaminodiphenyl ethane-3-carboxylic acid, 4,4'-diaminodiphenyl ether 3,3'-dicarboxylic acid, 4,4'-like diaminodiphenyl ether 3-carboxylic acid.

The amount of the specific diamine used in synthesizing the polyamic acid can be arbitrarily set according to the compound to be used. For example, when using the compound represented by the said Formula (d-1), it is preferable to set it as 10 mol% or more with respect to all the diamine, and it is more preferable to set it as 30 mol% or more. . Moreover, when using the compound represented by the said Formula (d-2), from the viewpoint of providing a low inclination-orientation angle with respect to a liquid crystal molecule, the amount used is 10 mol% or more with respect to all diamine It is preferable to set it as 30 mol% or more, It is more preferable to set it as 50 mol% or more.
When using the compound represented by the said Formula (d-3), it is preferable to make the usage-amount into 5 mol% or more with respect to all the diamines from a viewpoint of making stability of voltage retention favorable. And 10 mol% or more is more preferable.

When using at least one selected from the group consisting of a compound represented by the above formula (d-4) and a compound represented by the above formula (d-5), the use thereof from the viewpoint of imparting good orientation. The amount (the total amount of two or more compounds used) is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total diamine. In addition, as a specific diamine, 1 type of the compounds illustrated above can be used individually or in combination of 2 or more types.
When using carboxyl group-containing diamine as said other diamine, it is preferable to make the carboxyl group-containing diamine 5 mol% or more with respect to all the diamine, and, as for the usage ratio, 10-90 mol% is more preferable, An amount of 70 to 70 mol% is more preferable.

（式（ｍ−１）中、Ｒ^２３は、炭素数６〜２０のアルキル基又はアルコキシ基であり、Ｒ^２４は２価の有機基であり、ｈは０又は１である。） With regard to a liquid crystal aligning agent for a liquid crystal display element of TN type, in the synthesis of a polyamic acid, the following formula (A) together with a tetracarboxylic acid dianhydride and a diamine for the purpose of giving an appropriate inclined alignment angle to liquid crystal molecules. You may use the monoamine represented by m-1).

(In formula (m-1), R ²³ is an alkyl group having 6 to 20 carbon atoms or an alkoxy group, R ²⁴ is a divalent organic group, and h is 0 or 1.)

In the above formula (m-1), examples of the alkyl group having 6 to 20 carbon atoms of R ²³ include hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tridecyl, tetradecyl and pentadecyl And hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, eicosyl group and the like, which may be linear or branched. As a C6-C20 alkoxy group, the group (-OR < ²³ >) etc. which the C6-C20 alkyl group of the said illustration couple | bonded with the oxygen atom are mentioned, for example.

Examples of the divalent organic group in R ²⁴ include divalent hydrocarbon groups such as divalent chain hydrocarbon groups, alicyclic hydrocarbon groups and aromatic hydrocarbon groups, and carbon-carbon bonds in hydrocarbon groups. Among them, groups having functional groups such as -O-, -CO-, -COO-, -S- and the like, and heterocycle-containing groups can be mentioned. Here, specific examples of the divalent hydrocarbon group include, as a chain hydrocarbon group, a methylene group, ethylene group, propanediyl group, butanediyl group, pentanediyl group, hexanediyl group, heptanediyl group, octanediyl group, and the like Nonanediyl group, decanediyl group, undecanediyl group, dodecanediyl group, tridecanediyl group, tetradecanediyl group, tetradecanediyl group, pentadecanediyl group, octadecanediyl group, icosylene group, vinylene group, propenediyl group, butenediyl group, pentendiyl group, ethynylene group, propynylene group And the like; as an alicyclic hydrocarbon group, for example, cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cyclohexenylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclode Lene group, cycloundecylene group, cyclododecylene group, cyclotridecylene group, cyclotetradecylene group, cyclopentadecylene group, cyclooctadecylene group, cycloecosilene group, bicyclohexylene group, norbornylene group, adamantylene group, etc. Examples of the aromatic hydrocarbon group include phenylene group and biphenylene group. Among them, R ²⁴ is preferably a chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group.

  Preferred specific examples of the monoamine represented by the above formula (m-1) include, for example, n-hexylamine, n-octylamine, n-decylamine, n-dodecylamine, n-hexadecylamine, and 1,3-dimethyl Aliphatic monoamines such as butylamine, 1,5-dimethylhexylamine and 2-ethylhexylamine; p-aminophenylhexane, p-aminophenyloctane, p-aminophenyldodecane, p-aminophenylhexadecane, p-aminophenoxyoctane And aromatic monoamines such as p-aminophenoxydodecane and p-aminophenoxyhexadecane; and the like.

The proportion of the monoamine used is a mole of tetracarboxylic acid dianhydride used, a mole of diamine is b, and a monoamine is c from the viewpoint of suppressing that the monoamine liberated in the liquid crystal cell produced exerts an influence on the display characteristics. It is preferable to satisfy “2 (a−b) ≧ c> 0” in molar.
The monoamine represented by the above formula (m-1) may be reacted or polymerized with respect to the reaction product after the reaction of tetracarboxylic acid dianhydride and diamine, or tetracarboxylic acid The three components of the anhydride, diamine and monoamine may be reacted and polymerized simultaneously.

[Molecular weight regulator]
When synthesizing a polyamic acid, an end-modified polymer may be synthesized using an appropriate molecular weight modifier together with the above-described tetracarboxylic acid dianhydride and diamine. By using such a terminal-modified polymer, the coatability (printability) of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention.

As a molecular weight modifier, an acid monoanhydride, a monoamine compound, a monoisocyanate compound etc. can be mentioned, for example. As specific examples of these, as acid monoanhydride, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic acid As a monoamine compound, for example, aniline, cyclohexylamine, n-butylamine, a compound represented by the above formula (m-1), etc. as a monoamine compound; For example, phenyl isocyanate, naphthyl isocyanate and the like can be mentioned respectively.
The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total of tetracarboxylic acid dianhydride and diamine used.

<Synthesis of polyamic acid>
The ratio of tetracarboxylic acid dianhydride and diamine used in the synthesis reaction of the polyamic acid is 0.2 to 2 acid anhydride groups of tetracarboxylic acid dianhydride to 1 equivalent of amino group of diamine. The ratio which becomes equivalent is preferable, and the ratio which becomes 0.3-1.2 equivalent is more preferable.
The synthesis reaction of polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 to 100 ° C. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Here, examples of the organic solvent include aprotic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons and the like.
Specific examples of these organic solvents include, as the above aprotic polar solvent, for example, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, N, N -Dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide etc .; as the above-mentioned phenolic solvents eg phenol, m-cresol, xylenol, halogenated phenol etc. To

Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like; and examples of the ketone include acetone, Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone etc .; as the above ester, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate, malon Acid diethyl, isoamyl propionate, isoamyl isobutyrate etc;
Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol monomethyl ether , Diethylene glycol monomethyl ether acetate, tetrahydrofuran, diisopentyl ether etc .;
As the above-mentioned halogenated hydrocarbons, for example, dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene etc .; As the above-mentioned hydrocarbons, for example, hexane, heptane, octane, Benzene, toluene, xylene and the like can be mentioned respectively. In addition, a specific solvent (B) can also be used.

  Among these organic solvents, one or more selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvent A), or one or more selected from organic solvent A, an alcohol, a ketone, an ester, It is preferred to use a mixture with one or more selected from the group consisting of ether, halogenated hydrocarbon and hydrocarbon (organic solvent B). In the latter case, the use ratio of the organic solvent B is preferably 50% by weight or less, more preferably 40% by weight or less, still more preferably 30% by weight, based on the total amount of the organic solvent A and the organic solvent B. % Or less. The amount (a) of the organic solvent used is such that the total amount (b) of tetracarboxylic acid dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. Is preferred.

  As described above, a reaction solution in which the polyamic acid is dissolved is obtained. The reaction solution may be used as it is for the preparation of a composition such as a liquid crystal aligning agent, or the polyamic acid contained in the reaction solution may be isolated and then used for the preparation of a liquid crystal aligning agent or the like. The polyamic acid may be purified and then used for the preparation of a liquid crystal aligning agent or the like. When polyamic acid is subjected to dehydration ring closure to form a polyimide, the reaction solution may be subjected to dehydration ring closure reaction as it is, or polyamic acid contained in the reaction solution may be isolated and then subjected to dehydration ring closure reaction. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. The isolation and purification of the polyamic acid can be carried out according to known methods.

<Polyimide>
The polyimide according to the present embodiment can be obtained by dehydration ring closure and imidization of the polyamic acid synthesized as described above.

  The polyimide may be a completely imidated product obtained by dehydration and ring closure of all of the amic acid structures possessed by the precursor polyamic acid, and only a part of the amic acid structure is subjected to dehydration ring closure, and the amic acid structure It may be a partial imidate in which an imide ring structure coexists. It is preferable that the imidation ratio of the polyimide in this embodiment is 30% or more, It is more preferable that it is 40 to 99%, It is still more preferable that it is 50 to 99%. The imidation ratio is a percentage representing the ratio of the number of imide ring structures to the total number of amic acid structures of polyimide and the number of imide ring structures. Here, part of the imide ring may be an isoimide ring.

The dehydration ring closure of polyamic acid is preferably performed by a method of heating polyamic acid or a method of dissolving polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closure catalyst to this solution, and heating as necessary. . Among these, the latter method is preferred.
In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to a solution of the above polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride and the like can be used as the dehydrating agent. The amount of the dehydrating agent used is preferably 0.01 to 20 moles relative to 1 mole of the polyamic acid's amic acid structure. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydrating ring closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. As an organic solvent used for a dehydration ring-closing reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  Thus, a reaction solution containing a polyimide is obtained. This reaction solution may be used as it is for preparation of a composition such as a liquid crystal alignment agent, or may be used for preparation of a liquid crystal alignment agent etc after removing a dehydrating agent and a dehydrating ring closure catalyst from the reaction solution. After release, it may be used for preparation of a liquid crystal alignment agent or the like, or it may be used for preparation of a liquid crystal alignment agent after purifying an isolated polyimide. These purification procedures can be performed according to known methods.

<Polyamic acid ester>
The polyamic acid ester contained in the composition such as the liquid crystal aligning agent of the present embodiment includes, for example, [I] polyamic acid obtained by the above synthesis reaction, a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, etc. It can be obtained by the method of synthesis by reaction, the method of reacting [II] tetracarboxylic acid diester and diamine, and the method of reacting [III] tetracarboxylic acid diester dihalide and diamine.

  Here, examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; and phenols such as phenol and cresol. Further, as the halide, for example, methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like can be mentioned, and as the epoxy group-containing compound, For example, propylene oxide and the like can be mentioned. The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring-opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the above-mentioned polyamic acid using the above-mentioned alcohols. Also, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride. As a diamine used by method [II] and [III], the specific diamine and other diamine which were illustrated by the synthesis | combination of the said polyamic acid can be used, and it is preferable that a specific diamine is included. The polyamic acid ester may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

<Solution viscosity and weight average molecular weight>
The polyamic acid, the polyimide and the polyamic acid ester obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s when the solution is a solution having a concentration of 10% by weight, and is preferably 15 to 500 mPa.s. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above-mentioned polymer is a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone and the like). It is the value measured at 25 ° C. using an E-type viscometer.
The reduced viscosity is not particularly limited as long as it can form a uniform coating film, but is preferably 0.05 to 3.0 dl / g, and is 0.1 to 2.5 dl / g. Is more preferably 0.3 to 1.5 dl / g.
The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyamic acid, polyimide and polyamic acid ester contained in the composition such as liquid crystal aligning agent according to the present embodiment is 500 to 100,000. Is preferably, and more preferably 1,000 to 50,000.

«Solvent»
The composition and the liquid crystal aligning agent according to the present embodiment have a compound represented by the formula (b-1A), a compound represented by the formula (b-1B), and a table represented by the formula (b1) as solvent components. And a specific solvent (B) which is at least one selected from the group consisting of a compound represented by the formula (b2) and a compound represented by the above formula (b2). By including such a specific solvent (B) in a composition such as a liquid crystal aligning agent, the coating property of the liquid crystal aligning agent on a substrate can be improved.

<1> Compound Represented by the Above Formula (b-1A) By Including the Compound Represented by the Above Formula (b-1A) in a Composition such as a Liquid Crystal Alignment Agent, Application to a Substrate such as a Liquid Crystal Alignment Agent And the storage stability of the liquid crystal alignment agent and the like can be improved. In addition, good display quality can be maintained even when the frame of the liquid crystal display element is narrowed.

In the compounds represented by the above formula (b-1A), X and Y are each independently -COO- or -OCO-. A and C ¹ each independently represent a monovalent hydrocarbon group having 1 to 6 carbon atoms, preferably a linear or branched alkyl group having 1 to 4 carbon atoms. B is a C1-C12 bivalent hydrocarbon group, Preferably it is a C1-C6 alkylene group.

As a compound represented by the said Formula (b-1A), the thing shown below can be mentioned, for example. In addition, the compound represented by the said Formula (b-1A) may be used individually by 1 type, and may be used combining 2 or more types.

  Here, for example, the liquid crystal aligning agent is usually stored (for example, at -15 ° C) in a very low temperature environment to prevent deterioration of the polyamic acid and the polyimide during production and shipping. However, in the liquid crystal aligning agent stored at a low temperature for a long time, a precipitate may be generated in the solution. In addition, the precipitate once deposited is difficult to be dissolved again, which may cause problems such as printing failure in the manufacturing process of the liquid crystal display device. Although the cause of the generation of such precipitates is not clear, it is presumed that butyl cellosolve generally used as a solvent component of liquid crystal aligning agent is a cause. Therefore, it is required to find a new organic solvent to replace butyl cellosolve as a solvent for improving the coatability on a substrate.

  A liquid crystal display is manufactured by opposingly arranging a pair of substrates on which a liquid crystal alignment film is formed, and arranging liquid crystal between the pair of opposed substrates. At this time, the pair of substrates is bonded using a sealing agent such as epoxy resin. In touch panel display panels represented by smartphones and tablet PCs, attempts have been made to narrow the frame in order to make the movable area of the touch panel wider and to miniaturize the liquid crystal panel (element). With the narrowing of the frame of the liquid crystal panel, display unevenness may be visually recognized around the sealing agent, and the display quality was not sufficiently satisfactory. In order to achieve high definition and long life of a liquid crystal display, a liquid crystal display element in which display unevenness in the vicinity of such a sealing agent is hard to be recognized (a bezel unevenness resistance is high) is required.

  In this respect, the compound represented by the above formula (b-1A) is useful as a new organic solvent replacing butyl cellosolve. Specifically, a liquid crystal aligning agent containing a compound represented by the above formula (b-1A) as a solvent component is excellent in storage stability for a long period of low temperature storage and coatability to a substrate, and the frame is narrowed It corresponds to

<2> Compound Represented by the Formula (b-1B) The compound represented by the formula (b-1B) is contained in a composition such as a liquid crystal aligning agent, thereby applying a liquid crystal aligning agent or the like to a substrate And the storage stability of the liquid crystal alignment agent and the like can be improved. In addition, good display quality can be maintained even when the frame of the liquid crystal display element is narrowed.

The compound represented by the above formula ^{(b-1B), R 1} ~R 2 are each independently an alkyl group having 3 to 6 carbon atoms, preferably an alkyl group having 4-6 carbon atoms. Each R ³ is independently a hydrogen atom or a methyl group. n4 is 2 or 3;
When n4 is 2, it is preferable that both R ^{3 be} hydrogen atoms, or one be a hydrogen atom and the other be a methyl group, and it is particularly preferable that they be both hydrogen atoms.
When n ⁴ is ³ , all ^three R ^{3 s} are hydrogen atoms, or two hydrogen atoms and one methyl group are preferred, and all hydrogen atoms are particularly preferred.

As a compound represented by said Formula (b-1B), the thing shown below can be mentioned, for example. In addition, the compound represented by the said Formula (b-1B) may be used individually by 1 type, and may be used combining 2 or more types.

  The compound represented by the said Formula (b-1B) is useful as a new organic solvent replaced with butyl cellosolv like the said (b-1A). Specifically, a liquid crystal aligning agent containing a compound represented by the above formula (b-1B) as a solvent component is excellent in storage stability for a long period of low temperature storage and coatability to a substrate, and the frame is narrowed It corresponds to

<3> Compound Represented by Formula (b1) or Formula (b2) The compound represented by Formula (b1) or Formula (b2) has good solubility in polyamic acid and polyimide and a boiling point Moderately high. Therefore, by using such a compound as at least a part of the solvent, volatilization of the solvent from above the printing machine can be suppressed at the time of printing of the composition such as liquid crystal alignment agent on the substrate. It becomes difficult to precipitate the polymer component. As a result, printability (particularly long-term printability) can be improved. Moreover, since the boiling point of the solvent is not too high, when preheating (pre-baking) is performed after printing, the amount of solvent remaining in the coating film after preheating can be reduced. Therefore, it can suppress that dust adheres to the coating-film surface after preheating, and, thereby, can suppress the fall of the yield of a product.

(Compound represented by the above formula (b1))
About the compound represented by the said Formula (b1), R is a C1-C3 alkyl group, It is preferable that it is a C1-C2 alkyl group. n is an integer of 0 to 2, preferably 1 or 2.
As a compound represented by the said Formula (b1), the thing shown below can be mentioned, for example. In addition, the compound represented by the said Formula (b1) can be used individually by 1 type or in combination of 2 or more types.

(Compound represented by the above formula (b2))
About the compound represented by the said Formula (b2), m is an integer of 0-2, and it is preferable that it is 1 or 2.
As a compound represented by the said Formula (b2), the thing shown below can be mentioned, for example. In addition, the compound represented by the said Formula (b2) can be used individually by 1 type or in combination of 2 or more types.

  The specific solvent (B) contained in the composition or liquid crystal aligning agent of the present embodiment is a compound represented by the above formula (b-1A), a compound represented by the above formula (b-1B), and Or only one of the compounds represented by Formula (b1) or Formula (b2). Moreover, you may contain combining these 2 or more types.

(Other solvents)
It is preferable that compositions, such as a liquid crystal aligning agent of this embodiment, further contain other solvents other than the said specific solvent (B) as a solvent component. As the said other solvent, it is a poor solvent which can melt | dissolve a polymer (A) (henceforth a "1st solvent"), the said polymer (A), and is other than the said specific solvent (B) An organic solvent etc. can be mentioned.

  The first solvent may be a good solvent for the polymer (A), and preferred examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-pentyl-2 -Pyrrolidone, 3-methoxy-N, N-dimethylpropionamide, N, N, 2-trimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, γ-butyrolactone, γ-butyrolactam, N, N-dimethyl Examples include formamide, N, N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, dimethylsulfoxide, tetramethylurea, hexamethylphosphortriamide, m-cresol and the like. The first solvent may be used singly or in combination of two or more.

  Moreover, it is a poor solvent of the said polymer (A), and it is ethylene glycol monomethyl ether, a butyl lactate, an acetic acid, for example as organic solvents (Hereafter, it is also called "other poor solvents.") Other than the said specific solvent (B). Butyl, methyl methoxy propionate, ethyl ethoxy propionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol i-propyl ether, ethylene glycol n-butyl ether (butyl cellosolve ), Ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate Diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, ethylene carbonate, propylene carbonate, diacetone alcohol, diethylene glycol diethyl ether, diisopentyl ether, propylene glycol di An acetate etc. can be mentioned. The organic solvents may be used singly or in combination of two or more. In addition, below, the group which consists of said other poor solvents and a specific solvent (B) is also called "2nd solvent."

It is preferable that the content rate of the specific solvent (B) in a liquid crystal aligning agent is 1 to 70 weight% with respect to the total amount of the solvent contained in a liquid crystal aligning agent. When the content of the specific solvent (B) is less than 1% by weight, it is difficult to obtain the effect of improving the coatability on the substrate, and when it exceeds 70% by weight, the polymer component tends to precipitate. The content ratio of the specific solvent (B) is more preferably 5 to 70% by weight, still more preferably 10 to 65% by weight.
The content ratio of the first solvent is preferably 5% by weight or more, and more preferably, relative to the total amount of the solvent contained in the liquid crystal aligning agent, from the viewpoint of suppressing the precipitation of the polymer (A). It is 10% by weight or more, more preferably 15% by weight or more. In addition, the upper limit value of the content ratio of the first solvent is preferably 99 weight based on the total amount of the solvent contained in the liquid crystal aligning agent from the viewpoint of suitably obtaining the effect by the addition of the specific solvent (B). % Or less, more preferably 95% by weight or less, still more preferably 85% by weight or less.

The content ratio of the above-mentioned other poor solvents is preferably 70% by weight or less, more preferably 60% by weight or less, still more preferably 50% by weight or less based on the total amount of the solvents contained in the liquid crystal aligning agent. Particularly preferably, it is at most 30% by weight.
The ratio of the first solvent to the second solvent is such that the amount of use of the second solvent is 0.03 times (by weight) or more with respect to the amount of use of the first solvent from the viewpoint of improving the coatability on the substrate. Is preferred, and more preferably 0.05 times (by weight) or more. Further, from the viewpoint of suppressing the precipitation of the polymer, the amount is preferably 2.5 times (by weight) or less, and more preferably 2.0 times (by weight) or less.

  The liquid crystal aligning agent according to the present embodiment preferably contains substantially no butyl cellosolve as a solvent. In the present specification, the phrase "containing substantially no butyl cellosolve" means that the content ratio of butyl cellosolve is preferably 5% by weight or less, more preferably 3% by weight based on the total amount of the solvent contained in the liquid crystal aligning agent. It means that it is not more than% by weight, more preferably not more than 0.5% by weight.

<< Other ingredients >>
The composition such as the liquid crystal aligning agent according to the present embodiment contains the polymer (A) and the solvent as described above, but may contain other components as needed. Examples of such other components include polymers other than the above-mentioned polymer (A), compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy group-containing compounds”), functional silane compounds, The said amine compound (C) etc. can be mentioned.

[Other polymers]
The above-mentioned other polymers can be used to improve solution properties and electrical properties. Examples of such other polymers include polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates and the like. When the said other polymer is added to a liquid crystal aligning agent, 50 weight% or less is preferable with respect to the total amount of the polymer component in a liquid crystal aligning agent, and 0.1 to 40 weight% is more preferable Preferably, 0.1 to 30% by weight is more preferable.

[Epoxy group-containing compound]
An epoxy group containing compound can be used in order to improve adhesiveness with the substrate surface in a liquid crystal aligning film. Here, as the epoxy group-containing compound, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2, 2-dibromo neopentyl glycol diglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylene diamine 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodi Enirumetan, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - and cyclohexyl amine.
When these epoxy group-containing compounds are added to the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, and 0.1 to 30 parts by weight with respect to 100 parts by weight in total of the polymers contained in the liquid crystal aligning agent. Part is more preferred.

[Functional Silane Compound]
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Such functional silane compounds include, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) ) 3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl -3, 6- Methyl azanonanoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycide And xylpropyltrimethoxysilane and the like.
When adding these functional silane compounds to a liquid crystal aligning agent, 2 parts by weight or less is preferable with respect to a total of 100 parts by weight of the polymer, and 0.02 to 0.2 parts by weight is more preferable.

[Amine compound (C)]
The amine compound (C) has one primary amino group and a nitrogen-containing aromatic heterocyclic ring, and the primary amino group is bonded to a chain hydrocarbon group or an alicyclic hydrocarbon group It is a compound having a structure. The said amine compound (C) can be used in the liquid crystal aligning film use for the purpose of improving the electrical property (for example, voltage relaxation rate, relaxation rate of a residual charge, etc.) of a liquid crystal display element.

  The nitrogen-containing aromatic heterocyclic ring in the amine compound (C) may be an aromatic ring containing one or more nitrogen atoms in the ring skeleton. Therefore, the ring skeleton may contain only nitrogen atoms as hetero atoms, or may contain nitrogen atoms and hetero atoms other than nitrogen atoms (such as oxygen atoms and sulfur atoms). Specific examples of the nitrogen-containing aromatic heterocyclic ring include, for example, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, indole ring, benzimidazole ring, purine ring, quinoline ring , Isoquinoline ring, naphthyridine ring, quinoxaline ring, phthalazine ring, triazine ring, azepine ring, diazepine ring, acridine ring, phenazine ring, phenanthroline ring, oxazole ring, oxazole ring, thiazole ring, carbazole ring, thiadiazole ring, benzothiazole ring, phenothiazine ring, An oxadiazole ring etc. are mentioned. In addition, the nitrogen-containing aromatic heterocyclic ring may be one in which a substituent is introduced to a carbon atom constituting the ring exemplified above. As the said substituent, a halogen atom, an alkyl group, an alkoxy group etc. are mentioned, for example.

  The chain hydrocarbon group in the amine compound (C) preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The chain hydrocarbon group may be linear or branched, and may be saturated or unsaturated. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and still more preferably 3 to 10 carbon atoms.

（式（ｃ−１）中、Ａ^１は、鎖状炭化水素基又は脂環式炭化水素基を有する２価の有機基であり、Ａ^２は、窒素含有芳香族複素環である。ただし、式中の１級アミノ基は、Ａ^１が有する鎖状炭化水素基又は脂環式炭化水素基に結合している。） As said amine compound (C), the compound represented by following formula (c-1) can be used preferably.

(In Formula (c-1), A ¹ is a divalent organic group having a chain hydrocarbon group or an alicyclic hydrocarbon group, and A ² is a nitrogen-containing aromatic heterocycle. The primary amino group in the formula is bonded to the chain hydrocarbon group or alicyclic hydrocarbon group that A ¹ has.)

The formula for (c-1), the divalent organic group represented by ^{A 1,} for example, a divalent chain hydrocarbon group, a divalent alicyclic hydrocarbon ^{group, -O-R 21 -, -} CO -R ²¹ - (. ^{However, R 21} is a divalent a chain hydrocarbon group or an alicyclic hydrocarbon group). Moreover, the said bivalent organic group is -O-, -NH-, -CO-O-, between the carbon-carbon bond in a bivalent chain hydrocarbon group or a bivalent alicyclic hydrocarbon group. _{-CO-NH -, - CO -} , - S -, - S (O) 2 -, - Si (CH 3) 2 -, - O-Si (CH 3) 2 -, - O-Si (CH 3) _2— O—, a divalent group having an aromatic hydrocarbon group such as phenylene group, a heterocyclic group such as pyridinylene group, etc .; at least in a divalent chain hydrocarbon group or a divalent alicyclic hydrocarbon group A divalent group in which one hydrogen atom is substituted with a fluorine atom, a halogen atom such as chlorine atom, bromine atom or iodine atom, an aromatic hydrocarbon group such as phenyl group, a hydroxyl group, a halogenated alkyl group or the like; It may be The description of R ^{24 in} the formula (m-1) applies to specific examples of the divalent chain hydrocarbon group and the alicyclic hydrocarbon group in A ¹ .

Among the above, A ¹ is preferably a divalent organic group having a chain hydrocarbon group, and more preferably a divalent chain hydrocarbon group. A ¹ preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and still more preferably 1 to 10 carbon atoms. The above description applies for nitrogen-containing aromatic heterocycle A ^2.

As a specific example of the said amine compound (C), the compound etc. which are represented by each of following formula (c-1-1)-a formula (c-1-32) etc. are mentioned, for example. In addition, as an amine compound (C), 1 type of these can be used individually or in combination of 2 or more types.

  When the above-mentioned amine compound (C) is added to the liquid crystal aligning agent, the compounding ratio is 1 weight to the total 100 parts by weight of the polymer from the viewpoint of suitably obtaining the effect by the addition of the amine compound (C) The content is preferably at least 2 parts by weight, more preferably at least 2 parts by weight. Further, from the viewpoint of not impairing the stability of the liquid crystal aligning agent, the amount is preferably 20 parts by weight or less, more preferably 15 parts by weight or less, based on 100 parts by weight in total of the polymer.

  Other additives to be contained in the liquid crystal aligning agent include, in addition to the above, a compound having at least one oxetanyl group in the molecule, an antioxidant and the like. These use ratios can be suitably selected according to the additive to be used in the range which does not impair the effect of this invention.

When the above-mentioned amine compound (C) is contained as an additive in the liquid crystal aligning agent according to the present embodiment, the above-mentioned polymer (A) can be suitably improved in the electrical characteristics of the liquid crystal display element. It is preferable that at least a part of the group have a carboxyl group. In addition, the number of carboxyl groups contained in the polymer (A) is preferably 0.1 to 3 in average per repeating unit of the polymer (A), and is 0.3 to 2 Is more preferable, and 0.5 to 1.8 are more preferable.
The method for adjusting the number of carboxyl groups contained in the polymer (A) is not particularly limited. For example, (i) a method performed by adjusting the imidation ratio of polyimide, (ii) for synthesis of the polymer (A) The method etc. which are performed by adjusting the carboxyl group content of the diamine to be used are mentioned. Moreover, you may carry out by using together said (i) and (ii). From the viewpoint of increasing the degree of freedom of the imidation ratio of the polymer (A), it is preferable to use the method (ii).

  When the polymer (A) having a carboxyl group and the above-mentioned amine compound (C) are contained in the liquid crystal aligning agent, the compounding ratio of the amine compound (C) is 1 mol of carboxyl group which the polymer (A) has. It is preferable to set it as 0,01 to 2 mol, more preferable to set it as 0.05 to 1 mol, and further preferable to set it as 0.08 to 0.8 mol.

  The solid content concentration of the liquid crystal aligning agent according to the present embodiment (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc. However, it is preferably in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent according to the present embodiment is applied to the substrate surface as described later, and preferably heated to form a coating film which is a liquid crystal alignment film or a coating film which becomes a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by weight, the film thickness of the coating film becomes too small to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes too large to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating characteristics deteriorate. It becomes.

  The particularly preferred range of solid content concentration varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, in the case of spin coating, the solid concentration is preferably in the range of 1.5 to 4.5% by weight. In the case of the offset printing method, it is particularly preferable to set the solid concentration in the range of 3 to 9% by weight and thereby to set the solution viscosity in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1 to 8% by weight and thereby to set the solution viscosity in the range of 3 to 20 mPa · s. The temperature at the time of preparing the liquid crystal aligning agent of the present embodiment is preferably 10 to 50 ° C., more preferably 20 to 30 ° C.

«Liquid crystal alignment film and liquid crystal display device»
The liquid crystal aligning film which concerns on this embodiment is formed of the liquid crystal aligning agent prepared as mentioned above. Moreover, the liquid crystal display element which concerns on this embodiment comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The drive mode to which the liquid crystal display element is applied is not particularly limited, and can be applied to various drive modes such as TN type, STN type, IPS type, FFS type, VA type, and MVA type. Below, while demonstrating the manufacturing method of the liquid crystal display element which concerns on this embodiment, the manufacturing method of a liquid crystal aligning film is demonstrated in the description.

  The liquid crystal display element according to the present embodiment can be manufactured, for example, by the following steps (1) to (3). In step (1), the substrate used differs depending on the desired drive mode. The steps (2) and (3) are common to each drive mode.

[Step (1): Formation of a Coating]
First, the liquid crystal aligning agent of the present embodiment is coated on a substrate, and then the coated surface is heated to form a coating film on the substrate.
(1-1) When manufacturing a TN type, STN type or VA type liquid crystal display device, two substrates provided with the patterned transparent conductive film are made into a pair on the respective transparent conductive film forming surfaces, The liquid crystal aligning agent according to the present embodiment is preferably applied by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method. Here, as the substrate, for example, glass such as float glass and soda glass; transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate and poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ), etc. It can be used. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photo-etching after forming a non-patterned transparent conductive film, a method of using a mask having a desired pattern when forming a transparent conductive film, etc. be able to. At the time of application of the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound, functional titanium on the surface of the substrate surface on which the coating film is to be formed. A pretreatment for applying a compound or the like in advance may be performed.

  After application of the liquid crystal alignment agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied alignment agent. The prebake temperature is preferably 30 to 200 ° C., more preferably 40 to 150 ° C., and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a baking (post-baking) step is carried out for the purpose of completely removing the solvent and optionally thermally imidizing the amic acid structure present in the polymer. The baking (post-baking) temperature is preferably 80 to 300 ° C., more preferably 120 to 250 ° C. The post-baking time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

  (1-2) In the case of producing an IPS type or FFS type liquid crystal display element, an electrode is provided on the electrode formation surface of a substrate provided with an electrode made of a transparent conductive film or a metal film patterned in a comb shape The liquid crystal aligning agent which concerns on this embodiment is each apply | coated to one surface of the opposing board | substrate which is not carried out, Then, a coating film is formed by heating each application surface. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or metal film, the pretreatment of the substrate, and the preferred thickness of the coating film formed It is the same as (1-1). For example, a film made of a metal such as chromium can be used as the metal film.

  In any case of the above (1-1) and (1-2), after a liquid crystal aligning agent is applied on the substrate, a coating film to be an alignment film is formed by removing the organic solvent. At this time, in the case where the polymer contained in the liquid crystal aligning agent is a polyamic acid or an imidized polymer having an imide ring structure and an amic acid structure, further heating is carried out after the coating film is formed. A dehydration ring closure reaction may be allowed to proceed to form a more imidized coating.

[Step (2): Treatment for giving orientation ability]
In the case of producing a TN type, STN type, IPS type or FFS type liquid crystal display device, the coating film formed in the step (1) is subjected to a treatment for imparting liquid crystal alignment ability. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. As the treatment, for example, rubbing treatment is performed such that the coating film is rubbed in a fixed direction with a roll wound with a cloth made of fiber such as nylon, rayon, cotton, etc., or photo alignment treatment for irradiating polarized or non-polarized radiation Can be mentioned. On the other hand, when manufacturing a VA-type liquid crystal display element, the coating film formed in the above step (1) can be used as it is as a liquid crystal alignment film, but even if the coating film is subjected to an alignment ability imparting treatment. Good.

In the light alignment treatment, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used as radiation for irradiating the coating film. If the radiation is polarized, it may be linearly polarized or partially polarized. When the radiation used is linearly polarized light or partially polarized light, the irradiation may be performed from the direction perpendicular to the substrate surface, may be performed from an oblique direction, or may be performed in combination. In the case of irradiating non-polarized radiation, the direction of the irradiation is oblique.
As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. Ultraviolet light in a preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter, a diffraction grating or the like. The dose of radiation is preferably 100 to 50,000 J / m ² , more preferably 300 to 20,000 J / m ² . In addition, light irradiation of the coating may be performed while heating the coating to enhance the reactivity. The temperature upon heating is usually 30 to 250 ° C, preferably 40 to 200 ° C, and more preferably 50 to 150 ° C.

  The liquid crystal alignment film after rubbing treatment is further irradiated with ultraviolet light to a part of the liquid crystal alignment film to change the pretilt angle of a part of the liquid crystal alignment film, or The resist film may be formed on the portion, and the rubbing treatment may be performed in a direction different from the rubbing treatment described above, and then the resist film may be removed to make the liquid crystal alignment film have different liquid crystal alignment capabilities for each region. . In this case, it is possible to improve the visibility characteristics of the obtained liquid crystal display element. The liquid crystal alignment film suitable for a VA type liquid crystal display element can be suitably used also for a liquid crystal display element of PSA (Polymer sustained alignment) type.

[Step (3): Construction of Liquid Crystal Cell]
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal is disposed between two substrates disposed opposite to each other to manufacture a liquid crystal cell. For example, the following two methods may be mentioned to manufacture a liquid crystal cell.
The first method is a conventionally known method. First, two substrates are disposed opposite to each other with a gap (cell gap) in such a manner that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealing agent. After the liquid crystal is injected and filled in the cell gap partitioned by the above, the liquid crystal cell is manufactured by sealing the injection hole. The second method is a method called ODF (One Drop Fill) method. For example, a UV-curable sealing material is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and then liquid crystal is dropped on a predetermined number of places on the liquid crystal alignment film surface After that, the other substrate is pasted together so that the liquid crystal alignment film faces each other, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealing agent. . Regardless of which method is used, the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then gradually cooled to room temperature, thereby achieving flow alignment at the time of liquid crystal filling. It is desirable to remove.

As the sealing agent, for example, an epoxy resin containing a hardening agent and aluminum oxide spheres as a spacer can be used.
Examples of liquid crystals include nematic liquid crystals and smectic liquid crystals, among which nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl A cyclohexane type liquid crystal, a pyrimidine type liquid crystal, a dioxane type liquid crystal, a bicyclooctane type liquid crystal, a cubane type liquid crystal, or the like can be used. In addition, cholesteric liquid crystals such as colestil chloride, cholesteryl nonaate, cholesteryl carbonate, and the like; and chiral agents such as those sold under the trade names "C-15" and "CB-15" (manufactured by Merck). And ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutyl cinnamate may be added and used.

  And a liquid crystal display element can be obtained by bonding a polarizing plate together to the outer surface of a liquid crystal cell. As a polarizing plate to be bonded to the outer surface of a liquid crystal cell, a polarizing plate called a “H film” obtained by absorbing iodine while stretching and orienting polyvinyl alcohol is sandwiched between a cellulose acetate protective film or the H film itself The polarizing plate which consists of can be mentioned. In addition, when a rubbing process is performed with respect to a coating film, two board | substrates are opposingly arranged so that the rubbing direction in each coating film may mutually become a predetermined angle, for example, orthogonal or antiparallel.

  The liquid crystal display device according to the present embodiment can be effectively applied to various devices, and, for example, a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, a digital camera, a mobile phone, It can be used for display devices such as a smartphone, various monitors, and a liquid crystal television.

  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited to these examples.

In the following examples, the imidation ratio of the polyimide in the polymer solution and the solution viscosity of the polymer solution were measured by the following methods.
[Imidation rate of polyimide]
The solution of the polyimide was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference substance. The imidation ratio [%] was determined from the obtained ¹ H-NMR spectrum by the following formula (x).
Imidation ratio [%] = (1−A ¹ / A ² × α) × 100 (x)
(In the formula (x), A ¹ is a proton-derived peak area of an NH group appearing around a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a precursor of a polymer (polyamic acid It is the number ratio of other protons to one proton of NH group in).
Solution viscosity of polymer solution
The solution viscosity (mPa · s) of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer.
[Reference Example 1]

[Reference Example 1A]
In a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 0.60 g (2.0 mmol) of 1,3-bis (4-aminophenethyl) urea (BAPU) as a diamine, and p-phenylenediamine (p-PDA) ) 1.95 g (18.0 mmol) was added, 30 g of N-methyl-2-pyrrolidone (NMP) was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 3.70 g (18.9 mmol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CBDA) as tetracarboxylic acid dianhydride is added, and the solid content concentration is further increased. NMP was added so as to be 12% by weight, and the solution was stirred at room temperature for 4 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (PA-1).
NMP and a compound represented by the following formula (b-a) as the specific solvent (B) (hereinafter referred to as “compound (b-a)”) are added to this polyamic acid solution, and the solvent composition is NMP: compound The liquid crystal aligning agent (S1A) was prepared so that (ba) = 60: 40 (weight ratio) and the polyamic acid concentration would be 6.0% by weight.

[Reference Example 2A]
In 343.5 g of NMP was dissolved 19.2 g (0.098 mol) of CBDA as a tetracarboxylic acid dianhydride and 24.2 g (0.1 mol) of 1,5-bis (4-aminophenoxy) pentane as a diamine, It was made to react for time. The polymerization reaction proceeded easily and uniformly to obtain a polyamic acid (PA-2). To the NMP solution of this polyamic acid (PA-2), NMP and a compound represented by the following formula (b-b) as the specific solvent (B) (hereinafter referred to as "the compound (b-b)") are added The liquid crystal aligning agent (S2A) was prepared such that the solvent composition was NMP: compound (b-b) = 50: 50 (weight ratio), and the polyamic acid concentration was 6.0 wt%.

[Reference Example 3A]
22.42 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid dianhydride, and 18.73 g of 4,4′-diaminodiphenylamine (4,4′DADPA) as a diamine 0.094 mol) was mixed in 345.1 g of NMP and allowed to react at room temperature for 5 hours. The polymerization reaction proceeded easily and uniformly to obtain a polyamic acid (PA-3). To the NMP solution of this polyamic acid (PA-3) is added NMP and a compound represented by the following formula (b-c) as the specific solvent (B) (hereinafter referred to as "the compound (b-c)") The liquid crystal aligning agent (S3A) was prepared such that the solvent composition was NMP: compound (b-c) = 80: 20 (weight ratio), and the polyamic acid concentration was 6.0% by weight.

[Reference Example 4A]
6.5 g (0.06 mol) of p-PDA as diamine and 4- (4-trans-n-heptylcyclohexyl) phenoxy) -1,3-diaminobenzene (PCH7DAB, represented by the above formula (d-4-3) Compound (15.22 g (0.04 mol)) is dissolved in 165 g of NMP, and 19.41 g (0.099 mol) of CBDA as a tetracarboxylic acid dianhydride is added thereto and allowed to react at room temperature for 24 hours to obtain a polyamic acid (PA A solution containing -4) was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid (PA-4) was 40,000. NMP and a compound represented by the following formula (b-d) as the specific solvent (B) (hereinafter referred to as "compound (b-d)") are added to 30 g of this solution, and the solvent composition is NMP: compound (b) A liquid crystal aligning agent (S4A) having a concentration of 4.5% by weight was prepared.

[Reference Example 5A]
1.46 g (13.5 mmol) of p-PDA as a diamine and 0.78 g (1.50 mmol) of cholestanyl 3,5-diaminobenzoate are mixed in 20.0 g of NMP and CBDA 2. as tetracarboxylic dianhydride. While adding 85 g (14.5 mmol), 24.7 g of NMP was added and allowed to react at 25 ° C. for 5 hours to obtain a solution containing polyamic acid (PA-5). Subsequently, NMP and a compound represented by the following formula (b-e) as the specific solvent (B) (hereinafter referred to as "the compound (b-e)") are added to 40.0 g of the obtained polyamic acid solution, The liquid crystal aligning agent (S5A) was prepared so that the solvent composition was NMP: compound (b-e) = 75: 25 (weight ratio), and the polyamic acid concentration was 4.0% by weight.

[Reference Example 6A]
2.58 g (13.1 mmol) of CBDA as tetracarboxylic dianhydride and 5.0 g (13.1 mmol) of PCH7DAB as a diamine are dissolved in 43 g of NMP, stirred at 20 ° C. for 4 hours for reaction, and polyamic acid (PA-6) ) Was obtained. Then, NMP solution of the obtained polyamic acid (PA-6), NMP, and a compound represented by the following formula (b-f) as a specific solvent (B) (hereinafter referred to as compound (b-f)) The liquid crystal aligning agent (S6A) was prepared such that the solvent composition was NMP: compound (b-f) = 35: 65 (weight ratio) and the solid content concentration was 3.0% by weight.

[Reference Example 7A]
8.724 g (0.04 mol) pyromellitic dianhydride (PMDA) as tetracarboxylic acid dianhydride, 2.877 g (0.0266 mol) p-PDA as a diamine, and 4.567 g (0.012 mol) PCH 7 DAB as NMP 91 The mixture was reacted in 6 g at room temperature for 3 hours to prepare a solution containing polyamic acid (PA-7). To 25 g of this polyamic acid solution, NMP and a compound represented by the following formula (b-g) as the specific solvent (B) (hereinafter referred to as compound (b-g)) are added, and the solvent composition is NMP: compound ( Liquid crystal aligning agent (S7A) was prepared so that b-g) = 60:40 (weight ratio) and the solid content concentration would be 5.0% by weight.

[Reference Example 8A]
14.64 g (0.072 mol) of 2,4-diamino-N, N-diallylaniline as diamine, 2.96 g (0.016 mol) of n-dodecylamine as monoamine, and 15.69 g of CBDA as tetracarboxylic acid dianhydride (0.08 mol) was reacted in 300 g of NMP at room temperature for 4 hours to prepare a solution containing a polyamic acid intermediate (PA-8). NMP and a compound represented by the following formula (b-h) as the specific solvent (B) (hereinafter referred to as a compound (b-h)) are added to an NMP solution of this polyamic acid intermediate, and the solvent composition is NMP. : Compound (b-h) = 60: 40 (weight ratio), solid content concentration 6.0 weight% liquid crystal aligning agent (S8A) was prepared.

[Reference Example 9A]
Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride (BODA) as tetracarboxylic acid dianhydride (BODA) 4.50 g (0.018 mol) After reacting 0.68 g (0.0018 mol) of PCH7DAB and 1.75 g (0.0162 mol) of p-PDA as diamines in 39.3 g of NMP at room temperature, they were further reacted at 40 ° C. for 43 hours. NMP is added to 42 g of this polyamic acid solution to prepare a 1% by weight solution, 4.18 g of acetic anhydride and 6.48 g of pyridine are added thereto as an imidization catalyst, and the reaction is carried out at room temperature for 30 minutes and 120 ° C. for 2 hours. I did. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a white polyimide powder. It was 72% when the imidation ratio of the obtained polyimide powder (polyimide (PI-1)) was measured. NMP and compound (ba) as a specific solvent (B) are added to this powder and dissolved, and the solvent composition is NMP: compound (ba) = 50: 50 (weight ratio), solid content concentration 4.5 weight The liquid crystal aligning agent (S9A) was prepared to be%.

[Reference Comparative Examples 1A to 9A]
According to the solvent composition of the liquid crystal aligning agent, a polymer is synthesized in the same manner as in the above-mentioned reference examples 1A to 9A except that butyl cellosolve (BC) is used instead of the specific solvent (B) as the second solvent. The liquid crystal aligning agents (R1A) to (R9A) were obtained, respectively. Reference Comparative Example XA (X is an integer of 1 to 9) is an example corresponding to Reference Example XA. That is, in Reference Comparative Example XA, a liquid crystal aligning agent was prepared in the same manner as in Reference Example XA except that the same polymer as in Reference Example XA was synthesized and butyl cellosolve was used instead of the specific solvent (B).

[Reference Example 10A]
Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride (BODA) as tetracarboxylic acid dianhydride (BODA) 4.50 g (0.018 mol) And 2.34 g (0.0054 mol) of a compound (PBCH5DAB) represented by the above formula (d-4-2) as a diamine, and 1.92 g (0.0126 mol) of 3,5-diaminobenzoic acid (35DAB) as NMP 26. The reaction was carried out at room temperature in 3 g and then at 43 ° C. for 43 hours. NMP is added to 30 g of this polyamic acid solution to prepare a 6% by weight solution, and 2.4 g of acetic anhydride and 1.8 g of pyridine are added thereto as an imidization catalyst, and reacted for 30 minutes at room temperature and 4 hours at 110 ° C. I did. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a white polyimide powder. It was 72% when the imidation ratio of the obtained polyimide powder (polyimide (PI-2)) was measured. 0.6 g of this powder is dissolved in a mixed solvent of NMP and 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent, and compound (ba) as a specific solvent (B), It was a 6.0 wt% solution. To this solution is added 0.4 g of a 7.5 wt% NMP solution of 3-aminomethylpyridine (3-AMP) (corresponding to 0.03 g as 3-AMP), and the liquid crystal is stirred at 50 ° C. for 15 hours. An alignment agent (S10A) was obtained. In addition, the liquid crystal aligning agent was prepared so that a solvent composition might be set to NMP: D1: compound (ba) = 30:20:50 (weight ratio).

[Reference Example 11A]
The same as Reference Example 10A except that the amount of PBCH5DAB used for the synthesis of polyamic acid was changed to 3.90 g (0.0090 mol) and the amount of 3,5-diaminobenzoic acid to 1.37 g (0.0090 mol). The operation was performed to obtain a polyamic acid solution. Moreover, using the obtained polyamic acid solution, the same operation as in Reference Example 10A was performed to obtain a polyimide powder. It was 74% when the imidation ratio of the obtained polyimide powder (polyimide (PI-3)) was measured. 0.6 g of this powder is dissolved in a mixed solvent of NMP and 3-butoxy-N, N-dimethylpropionamide (D2) as a first solvent and the compound (b-b) as a specific solvent (B), It was a 6.0 wt% solution. To this solution is added 0.8 g of a 7.5 wt% NMP solution of 3-aminomethylpyridine (3-AMP) (corresponding to 0.06 g as 3-AMP), and the liquid crystal is stirred at 50 ° C. for 15 hours. An alignment agent (S11A) was obtained. In addition, the liquid crystal aligning agent was prepared so that a solvent composition might be set to NMP: D2: compound (bb) = 30:30:40 (weight ratio).

[Reference Example 12A]
A solution containing polyamic acid (PA-1) was prepared in the same manner as in Reference Example 1A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent and compound (b-c) as a specific solvent (B), and the solvent composition is D1: compound (b) -C) = 60: 40 (weight ratio), solid content concentration 6.0 weight% liquid crystal aligning agent (S12A) was obtained.
[Reference Example 13A]
A solution containing polyamic acid (PA-2) was prepared in the same manner as in Reference Example 2A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-butoxy-N, N-dimethylpropionamide (D2) as the first solvent and the compound (b-d) as the specific solvent (B), and the solvent composition is D2: compound (b -D) = 50: 50 (weight ratio), the liquid crystal aligning agent (S13A) of polyamic acid concentration 6.0 weight% was obtained.

[Reference Example 14A]
A solution containing polyamic acid (PA-3) was prepared in the same manner as in Reference Example 3A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of NMP and 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent, and compound (b-e) as a specific solvent (B), and the solvent composition is NMP: D1: Compound (b-e) = 40: 40: 20 (weight ratio), a liquid crystal aligning agent (S14A) having a polyamic acid concentration of 6.0% by weight was obtained.
[Reference Example 15A]
A solution containing polyamic acid (PA-4) was prepared in the same manner as in Reference Example 4A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder and N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (E1) as an additive and NMP and 3-butoxy-N, N-dimethylpropionamide as a first solvent The solvent composition is dissolved in a mixed solvent of (D2) and the compound (b-f) as the specific solvent (B), and the solvent composition is NMP: D2: compound (b-f) = 40: 40: 20 (weight ratio), polyamic acid A liquid crystal aligning agent (S15A) having a concentration of 6.0% by weight was obtained. The amount of the additive (E1) used was 5 parts by weight with respect to the polyamic acid powder.

[Reference Example 16A]
A solution containing polyamic acid (PA-5) was prepared in the same manner as in Reference Example 5A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-methoxy-N, N-dimethylpropionamide (D1) as the first solvent and the compound (b-g) as the specific solvent (B), and the solvent composition is D1: compound (b A liquid crystal aligning agent (S16A) with a polyamic acid concentration of 6.0% by weight was obtained.
[Reference Example 17A]
A solution containing polyamic acid (PA-6) was prepared in the same manner as in Reference Example 6A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-butoxy-N, N-dimethylpropionamide (D2) as the first solvent and the compound (b-h) as the specific solvent (B), and the solvent composition is D2: compound (b) -H) = 35: 65 (weight ratio), polyamic acid concentration 6.0 weight% liquid crystal aligning agent (S17A) was obtained.

[Reference Example 18A]
A solution containing polyamic acid (PA-7) was prepared in the same manner as in Reference Example 7A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of NMP and γ-butyl lactone (D3) as the first solvent and the compound (ba) as the specific solvent (B), and the solvent composition is NMP: D3: compound (ba) ) = 30:30:40 (weight ratio), a liquid crystal aligning agent (S18A) with a polyamic acid concentration of 6.0% by weight was obtained.
[Reference Example 19A]
A solution containing a polyamic acid intermediate (PA-8) was prepared in the same manner as in Reference Example 8A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of NMP and 3-butoxy-N, N-dimethylpropionamide (D2) as a first solvent and the compound (b-b) as a specific solvent (B), and the solvent composition is NMP: D2: Compound (b-b) = 30: 30: 40 (weight ratio), and a liquid crystal aligning agent (S19A) having a polyamic acid concentration of 6.0% by weight was obtained.
[Reference Example 20A]
A powder of polyimide (PI-1) was obtained in the same manner as in Reference Example 9A. This powder is dissolved in a mixed solvent of 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent and compound (b-c) as a specific solvent (B), and the solvent composition is D1: compound (b) -C) = 50: 50 (weight ratio), solid content concentration 6.0 weight% liquid crystal aligning agent (S20A) was obtained.

<Evaluation of storage stability>
About each liquid crystal aligning agent obtained above, after filtering with a 1.0 micrometer filter, after storing for 1 month at -30 degreeC, it returns to room temperature (25 degreeC), and the presence or absence of the precipitate in a liquid crystal aligning agent is I observed it. The results are shown in Tables 1 and 2 below. In Tables 1 and 2, the case where no precipitate was observed in the liquid crystal aligning agent was shown as “○”, and the case where the precipitate was observed was shown as “x”.

<Evaluation of printability>
About each liquid crystal aligning agent prepared above, after filtering with a 1.0 micrometer filter, after storing for 6 months at -15 degreeC, it returned to room temperature (25 degreeC). Subsequently, the liquid crystal aligning agent was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of ITO films using liquid crystal aligning film printing machine (made by Nippon Photo Printing Co., Ltd. product). Thereafter, the solvent is removed by heating (pre-baking) on a hot plate at 80 ° C. for 1 minute, and then heating (post-baking) on a hot plate at 200 ° C. for 10 minutes to obtain a coating It formed. The coated film was observed with a microscope with a magnification of 20 times to examine the presence or absence of printing unevenness and pinholes. The evaluation was carried out with good printability (○) when print unevenness and pinholes were hardly observed as poor printability (×) when at least one of print unevenness and pinholes was observed. The results are shown in Tables 1 and 2 below.

In addition, the abbreviation in Table 1 and Table 2 is as follows.
(Acid dianhydride)
AN-1; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride AN-2; 2,3,5-tricarboxycyclopentylacetic acid dianhydride AN-3; pyromellitic acid dianhydride AN-4; Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride (diamine)
DA-1: 1,5-bis (4-aminophenoxy) pentane DA-2: 2,4-diamino-N, N-diallylaniline DA-3: cholestanyl 3,5-diaminobenzoate 35DAB: 3,5- Diaminobenzoic acid (monoamine)
MA-1: n-dodecylamine (first solvent)
D1: 3-methoxy-N, N-dimethylpropionamide D2: 3-butoxy-N, N-dimethylpropionamide D3: γ-butyl lactone (second solvent)
BC: butyl cellosolve (additive)
3-AMP: 3-aminomethylpyridine (compound represented by the above formula (c-1-16))
E1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

<Manufacture and evaluation of light alignment FFS liquid crystal display device>
(1) Production of FFS-Type Liquid Crystal Display Device Using Photoalignment Method An FFS-type liquid crystal display device 10 shown in FIG. 1 was produced. First, a glass substrate 11a having an electrode pair on one side of which is formed a bottom electrode 15 not having a pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape in this order The liquid crystal aligning agent (S1A) obtained above is used as an ink jet coating method on the surface of the glass substrate 11a having the transparent electrode and the one surface of the opposite glass substrate 11b. A coating was formed. As to the liquid crystal aligning agent (S1A), the viscosity of the solvent is 18 cP while keeping the solvent composition as “NMP: compound (ba) = 60: 40 (weight ratio)” before applying onto the substrate. The prepared and viscosity-adjusted liquid crystal aligning agent was applied onto the substrate.
Next, this coated film is prebaked on a hot plate at 80 ° C. for 1 minute, and then heated (post-baked) at 230 ° C. for 15 minutes in a nitrogen-replaced oven for 15 minutes. A coating was formed. A schematic plan view of the top electrode 13 used here is shown in FIG. 2 (a) is a top view of the top electrode 13, and FIG. 2 (b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2 (a). In this reference example, a substrate having a top electrode in which the line width d1 of the electrodes is 4 μm and the distance d2 between the electrodes is 6 μm was used. As the top electrode 13, four drive electrodes of an electrode A, an electrode B, an electrode C, and an electrode D were used. The structure of the drive electrode of this liquid crystal display element is shown in FIG. In this case, the bottom electrode 15 functions as a common electrode acting on all of the four drive electrodes, and each of the four drive electrode regions is a pixel region.

Next, each surface of the coating film is irradiated with polarized ultraviolet light 300 J / m ² including a bright line of 313 nm from the substrate normal direction using an Hg-Xe lamp and a Glan-Taylor prism, respectively, and a pair having a liquid crystal alignment film I got the substrate. At this time, the direction of irradiation of polarized ultraviolet light is from the normal direction of the substrate, and the direction of polarization plane is set so that the direction of the line segment of the polarization plane of polarized ultraviolet light projected onto the substrate is the direction of double-headed arrow in FIG. The light irradiation process was performed.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied by screen printing to the outer periphery of the surface having the liquid crystal alignment film of one of the substrates described above, and then the liquid crystal alignment film surfaces of the pair of substrates are It was made to face each other, superimposed so that the direction of polarization plane of polarized ultraviolet light projected onto the substrate was parallel, and pressed, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, liquid crystal injection port was filled with liquid crystal “MLC-6221” manufactured by Merck from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, this was heated to 150 ° C. and then gradually cooled to room temperature in order to remove the flow alignment at the time of liquid crystal injection.
Next, polarizing plates were attached to both outer sides of the substrate to produce an FFS liquid crystal display element. At this time, one of the polarizing plates is attached so that the polarization direction is parallel to the projection direction of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film on the substrate surface, and the other has its polarization direction first. It stuck so as to be orthogonal to the polarization direction of the polarizing plate.
The above method is repeated to manufacture a total of five FFS liquid crystal display elements, one for evaluation of liquid crystal alignment, evaluation of voltage holding ratio, evaluation of heat resistance, bezel unevenness resistance, and evaluation of afterimage characteristics as described below. Provided. However, in all cases, ultraviolet irradiation was not performed under voltage application.

(2) Evaluation of Liquid Crystal Alignment With the FFS liquid crystal display device manufactured above, the presence or absence of abnormal domain in the change of light and dark when the voltage of 5 V is turned ON / OFF (applied / canceled) is observed with a magnification of 50 times did. In the evaluation, the case where no abnormal domain was observed was regarded as “good” in liquid crystal alignment, and the case where an abnormal domain was observed was regarded as “defective” in liquid crystal alignment. In this liquid crystal display element, the liquid crystal alignment was "good".
(3) Evaluation of voltage holding ratio After applying a voltage of 5 V at a temperature of 23 ° C. for 60 microseconds and a span of 167 milliseconds for the FFS type liquid crystal display device manufactured above, 167 milliseconds after release of application. The voltage holding ratio (VHR) was measured to be 99.4%. In addition, as a measuring apparatus, Toyo Co., Ltd. make and VHR-1 were used.
(4) Evaluation of heat resistance The voltage holding ratio was measured in the same manner as the evaluation of the above (3) voltage holding ratio, and the value was used as the initial VHR (VHR _BF ). Then, the liquid crystal display element after the initial VHR measurement was allowed to stand in an oven at 100 ° C. for 500 hours. Thereafter, the liquid crystal display element was allowed to stand at room temperature and allowed to cool to room temperature, and then the voltage retention was measured in the same manner as described above, and the value was taken as VHR _AF . Moreover, the change rate ((DELTA) VHR (%)) of the voltage retention before and behind provision of heat stress was calculated | required by the following numerical formula (EX-2).
V VHR (%) = ((VHR _BF- VHR _AF ) ÷ VHR _BF ) × 100 ... (EX-2)
The heat resistance is evaluated as heat resistance “good” when change rate ΔVHR is less than 4%, heat resistance “good” when it is 4% or more and less than 5%, heat resistance when it is 5% or more It went as sex "defective". As a result, ΔVHR was 2.9%, and the heat resistance of this liquid crystal display element was “good”.

(5) Non-uniformity resistance around bezel (bezel unevenness resistance)
The FFS-type liquid crystal display device manufactured above was stored for 30 days under conditions of 25 ° C. and 50% RH, and then was driven at an alternating voltage of 5 V to observe the lighting state. The evaluation is "excellent" if no luminance difference (more black or more white) is visually recognized around the sealing agent, but it is recognized if the luminance difference disappears within 5 minutes after lighting, "good", 5 minutes If the difference in brightness disappears within 20 minutes, the case where the difference in brightness is visible even after 20 minutes is regarded as "defective". As a result, in this liquid crystal display element, no luminance difference was visually recognized around the sealing agent, and it was determined that bezel unevenness resistance was "excellent".
(6) Evaluation of afterimage characteristics (DC afterimage evaluation)
The photo-aligned FFS liquid crystal display device manufactured above was placed under an environment of 25 ° C. and 1 atmospheric pressure. The potential of the bottom electrode was set to a 0 V potential (ground potential), with the bottom electrode as a common electrode for all the four drive electrodes. The electrode B and the electrode D were short-circuited with the common electrode to apply 0 V, and a combined voltage of 3.5 V AC and 1 V DC was applied to the electrodes A and C for 2 hours. After 2 hours, a voltage of AC 1.5 V was immediately applied to all of the electrodes A to D. Then, from the time when a voltage of 1.5 V AC is started to be applied to all the drive electrodes, the drive stress application area (pixel area of the electrodes A and C) and the drive stress non-application area (pixel areas of the electrodes B and D) The time until the difference in brightness between the two and can not be visually confirmed was measured, and this was taken as the residual image elimination time. Note that, as this time is shorter, it is more difficult to cause an afterimage. The case where the residual image erasing time was less than 30 seconds was evaluated as “good”, the case where it was 30 seconds or more and less than 120 seconds as “good”, and the case where it was 120 seconds or more as “defective”. The residual image erasing time of the liquid crystal display element of 1 was 1 second, and the residual image characteristic was evaluated as "good".

From the above results, the liquid crystal aligning agents of the reference examples using the specific solvent (B) were all good in storage stability when stored at low temperature and also good in printability after low temperature storage. On the other hand, the liquid crystal aligning agent of the reference comparative example was inferior in the storage stability and the printability after low temperature storage. From this, it was found that, by using the specific solvent (B), the storage stability can be improved while securing the coating property on the substrate.
[Reference Example 2]

[Reference Example 1B]
In a 50 ml four-necked flask equipped with a stirrer and a nitrogen inlet tube, 0.60 g (2.0 mmol) of 1,3-bis (4-aminophenethyl) urea (BAPU) as a diamine, and p-phenylenediamine (p-PDA) ) 1.95 g (18.0 mmol) was added, 30 g of N-methyl-2-pyrrolidone (NMP) was added, and the mixture was stirred and dissolved while feeding nitrogen. While stirring this diamine solution, 3.70 g (18.9 mmol) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride (CBDA) as tetracarboxylic acid dianhydride is added, and the solid content concentration is further increased. NMP was added so as to be 12% by weight, and the solution was stirred at room temperature for 4 hours under a nitrogen atmosphere to obtain a solution of polyamic acid (PA-1).
NMP and a compound (2b-a) represented by the following formula (2b-a) as a specific solvent (B) are added to this polyamic acid solution, and the solvent composition is NMP: compound (2b-a) = 60: 40. (Weight ratio) A liquid crystal aligning agent (S1B) was prepared so that the polyamic acid concentration would be 6.0% by weight.

[Reference Example 2B]
In 343.5 g of NMP was dissolved 19.2 g (0.098 mol) of CBDA as a tetracarboxylic acid dianhydride and 24.2 g (0.1 mol) of 1,5-bis (4-aminophenoxy) pentane as a diamine, It was made to react for time. The polymerization reaction proceeded easily and uniformly to obtain a polyamic acid (PA-2). NMP and the compound (2b-a) as a specific solvent (B) are added to the NMP solution of this polyamic acid (PA-2), and the solvent composition is NMP: compound (2b-a) = 50: 50 (weight ratio) The liquid crystal aligning agent (S2B) was prepared such that the polyamic acid concentration was 6.0% by weight.

[Reference Example 3B]
22.42 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic acid dianhydride, and 18.73 g of 4,4′-diaminodiphenylamine (4,4′DADPA) as a diamine 0.094 mol) was mixed in 345.1 g of NMP and allowed to react at room temperature for 5 hours. The polymerization reaction proceeded easily and uniformly to obtain a polyamic acid (PA-3). NMP and the compound (2b-a) as a specific solvent (B) are added to an NMP solution of this polyamic acid (PA-3), and the solvent composition is NMP: compound (2b-a) = 80: 20 (weight ratio) The liquid crystal aligning agent (S3B) was prepared such that the polyamic acid concentration was 6.0% by weight.

[Reference Example 4B]
6.5 g (0.06 mol) of p-PDA as diamine and 4- (4-trans-n-heptylcyclohexyl) phenoxy) -1,3-diaminobenzene (PCH7DAB, represented by the above formula (d-4-3) Compound (15.22 g (0.04 mol)) is dissolved in 165 g of NMP, and 19.41 g (0.099 mol) of CBDA as a tetracarboxylic acid dianhydride is added thereto and allowed to react at room temperature for 24 hours to obtain a polyamic acid (PA A solution containing -4) was obtained. The weight average molecular weight (Mw) of the obtained polyamic acid (PA-4) was 40,000. To 30 g of this solution, NMP, diethylene glycol diethyl ether (DEDG) and compound (2b-a) as a specific solvent (B) are added, and the solvent composition is NMP: DEDG: compound (2b-a) = 80: 10: 10 (weight A liquid crystal aligning agent (S4B) having a concentration of 4.5% by weight was prepared.

[Reference Example 5B]
1.46 g (13.5 mmol) of p-PDA and 0.78 g (1.50 mmol) of cholestanyl 3,5-diaminobenzoate (DA-3) as diamines are mixed in 20.0 g of NMP to obtain tetracarboxylic acid dianhydride While adding 2.85 g (14.5 mmol) of CBDA as a substance, 24.7 g of NMP was added and allowed to react at 25 ° C. for 5 hours to obtain a solution containing polyamic acid (PA-5). Subsequently, NMP and the compound (2b-a) as a specific solvent (B) are added to 40.0 g of the obtained polyamic acid solution, and the solvent composition is NMP: compound (2b-a) = 75: 25 (weight ratio) The liquid crystal aligning agent (S5B) was prepared such that the polyamic acid concentration was 4.0% by weight.

[Reference Example 6B]
2.58 g (13.1 mmol) of CBDA as tetracarboxylic dianhydride and 5.0 g (13.1 mmol) of PCH7DAB as a diamine are dissolved in 43 g of NMP, stirred at 20 ° C. for 4 hours for reaction, and polyamic acid (PA-6) ) Was obtained. Then, NMP and the compound (2b-a) as a specific solvent (B) are added to the NMP solution of the obtained polyamic acid (PA-6), and the solvent composition is NMP: compound (2b-a) = 35: 65 The liquid crystal aligning agent (S6B) was prepared so that the solid content concentration was 3.0% by weight (weight ratio).

[Reference Example 7B]
8.724 g (0.04 mol) pyromellitic dianhydride (PMDA) as tetracarboxylic acid dianhydride, 2.877 g (0.0266 mol) p-PDA as a diamine, and 4.567 g (0.012 mol) PCH 7 DAB as NMP 91 The mixture was reacted in 6 g at room temperature for 3 hours to prepare a solution containing polyamic acid (PA-7). NMP and a compound represented by the following formula (2b-b) (hereinafter referred to as "compound (2b-b)") as a specific solvent (B) are added to 25 g of this polyamic acid solution, and the solvent composition is NMP: The liquid crystal aligning agent (S7B) was prepared such that the compound (2b-b) = 60: 40 (weight ratio) and the solid content concentration become 5.0% by weight.

[Reference Example 8B]
14.64 g (0.072 mol) of 2,4-diamino-N, N-diallylaniline as diamine, 2.96 g (0.016 mol) of n-dodecylamine as monoamine, and 15.69 g of CBDA as tetracarboxylic acid dianhydride (0.08 mol) was reacted in 300 g of NMP at room temperature for 4 hours to prepare a solution containing a polyamic acid intermediate (PA-8). NMP and the compound (2b-a) as a specific solvent (B) are added to an NMP solution of this polyamic acid intermediate, and the solvent composition is NMP: compound (2b-a) = 60: 40 (weight ratio), solid content A liquid crystal aligning agent (S8B) having a concentration of 6.0% by weight was prepared.

[Reference Example 9B]
Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride (BODA) as tetracarboxylic acid dianhydride (BODA) 4.50 g (0.018 mol) After reacting 0.68 g (0.0018 mol) of PCH7DAB and 1.75 g (0.0162 mol) of p-PDA as diamines in 39.3 g of NMP at room temperature, they were further reacted at 40 ° C. for 43 hours. NMP is added to 42 g of this polyamic acid solution to prepare a 1% by weight solution, 4.18 g of acetic anhydride and 6.48 g of pyridine are added thereto as an imidization catalyst, and the reaction is carried out at room temperature for 30 minutes and 120 ° C. for 2 hours. I did. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a white polyimide powder. It was 72% when the imidation ratio of the obtained polyimide powder (polyimide (PI-1)) was measured. NMP and the compound (2b-a) as a specific solvent (B) are added to this powder and dissolved, and the solvent composition is NMP: compound (2b-a) = 50: 50 (weight ratio), solid content concentration 4.5 weight The liquid crystal aligning agent (S9B) was prepared to be%.

[Reference Comparative Examples 1B, 3B to 9B]
With respect to the solvent composition of the liquid crystal aligning agent, the polymer is synthesized in the same manner as the reference examples 1B and 3B to 9B except that butyl cellosolve (BC) is used in place of the specific solvent (B) as the second solvent. The agents were prepared to obtain liquid crystal aligning agents (R1B) and (R3B) to (R9B), respectively.
[Reference Comparative Example 2B]
According to the solvent composition of the liquid crystal aligning agent, a polymer is synthesized and a liquid crystal aligning agent is prepared in the same manner as in Reference Example 2B except that ethylene glycol dimethyl ether is used instead of the specific solvent (B) as the second solvent. A liquid crystal aligning agent (R2B) was obtained.
Reference Comparative Example XB (X is an integer of 1 to 9) is an example corresponding to Reference Example XB. That is, in Reference Comparative Example XB, a liquid crystal aligning agent was prepared in the same manner as in Reference Example XB except that the same polymer as in Reference Example XB was synthesized, and butyl cellosolve or ethylene glycol dimethyl ether was used instead of the specific solvent (B). .

[Reference Example 10B]
Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride (BODA) as tetracarboxylic acid dianhydride (BODA) 4.50 g (0.018 mol) And 2.34 g (0.0054 mol) of a compound (PBCH5DAB) represented by the above formula (d-4-2) as a diamine, and 1.92 g (0.0126 mol) of 3,5-diaminobenzoic acid (35DAB) as NMP 26. The reaction was carried out at room temperature in 3 g and then at 43 ° C. for 43 hours. NMP is added to 30 g of this polyamic acid solution to prepare a 6% by weight solution, and 2.4 g of acetic anhydride and 1.8 g of pyridine are added thereto as an imidization catalyst, and reacted for 30 minutes at room temperature and 4 hours at 110 ° C. I did. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a white polyimide powder. It was 72% when the imidation ratio of the obtained polyimide powder (polyimide (PI-2)) was measured. 0.6 g of this powder is dissolved in a mixed solvent of NMP and 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent, and compound (2b-a) as a specific solvent (B), It was a 6.0 wt% solution. To this solution is added 0.4 g of a 7.5 wt% NMP solution of 3-aminomethylpyridine (3-AMP) (corresponding to 0.03 g as 3-AMP), and the liquid crystal is stirred at 50 ° C. for 15 hours. An alignment agent (S10B) was obtained. The liquid crystal aligning agent was prepared such that the solvent composition was NMP: D1: compound (2b-a) = 30: 20: 50 (weight ratio).

[Reference Example 11B]
The same as Reference Example 10B except that the amount of PBCH5DAB used for the synthesis of polyamic acid was changed to 3.90 g (0.0090 mol) and the amount of 3,5-diaminobenzoic acid to 1.37 g (0.0090 mol). The operation was performed to obtain a polyamic acid solution. Further, using the obtained polyamic acid solution, the same operation as in Reference Example 10B was performed to obtain a polyimide powder. It was 74% when the imidation ratio of the obtained polyimide powder (polyimide (PI-3)) was measured. 0.6 g of this powder is dissolved in a mixed solvent of NMP and 3-butoxy-N, N-dimethylpropionamide (D2) as the first solvent and the compound (2b-b) as the specific solvent (B) It was a 6.0 wt% solution. To this solution is added 0.8 g of a 7.5 wt% NMP solution of 3-aminomethylpyridine (3-AMP) (corresponding to 0.06 g as 3-AMP), and the liquid crystal is stirred at 50 ° C. for 15 hours. An alignment agent (S11B) was obtained. In addition, the liquid crystal aligning agent was prepared so that a solvent composition might be NMP: D2: compound (2b-b) = 30:30:40 (weight ratio).

[Reference Example 12B]
A solution containing polyamic acid (PA-1) was prepared in the same manner as in Reference Example 1A. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent and compound (2b-b) as a specific solvent (B), and the solvent composition is D1: compound (2b) -B) = 60: 40 (weight ratio), solid content concentration 6.0 weight% liquid crystal aligning agent (S12B) was obtained.
[Reference Example 13B]
A solution containing polyamic acid (PA-2) was prepared in the same manner as in Reference Example 2B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-butoxy-N, N-dimethylpropionamide (D2) as a first solvent and compound (2b-a) as a specific solvent (B), and the solvent composition is D2: compound (2b) Liquid crystal aligning agent (S13B) of -a) = 50: 50 (weight ratio) and polyamic acid concentration 6.0 weight% was obtained.

[Reference Example 14B]
A solution containing polyamic acid (PA-3) was prepared in the same manner as in Reference Example 3B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of NMP and 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent and the compound (2b-a) as a specific solvent (B), and the solvent composition is NMP: D1: Compound (2b-a) = 40: 40: 20 (weight ratio), a liquid crystal aligning agent (S14B) having a polyamic acid concentration of 6.0% by weight was obtained.
[Reference Example 15B]
A solution containing polyamic acid (PA-4) was prepared in the same manner as in Reference Example 4B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder and N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (E1) as an additive and NMP and 3-butoxy-N, N-dimethylpropionamide as a first solvent The solvent composition is dissolved in a mixed solvent of (D2) and compound (2b-a) as the specific solvent (B), and the solvent composition is NMP: D2: compound (2b-a) = 40: 40: 20 (weight ratio), polyamic acid A liquid crystal aligning agent (S15B) having a concentration of 6.0% by weight was obtained. The amount of the additive (E1) used was 5 parts by weight with respect to the polyamic acid powder.

[Reference Example 16B]
A solution containing polyamic acid (PA-5) was prepared in the same manner as in Reference Example 5B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent and compound (2b-a) as a specific solvent (B), and the solvent composition is D1: compound (2b) The liquid crystal aligning agent (S16B) of -a) = 75:25 (weight ratio) and polyamic acid concentration 6.0 weight% was obtained.
[Reference Example 17B]
A solution containing polyamic acid (PA-6) was prepared in the same manner as in Reference Example 6B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of 3-butoxy-N, N-dimethylpropionamide (D2) as a first solvent and compound (2b-a) as a specific solvent (B), and the solvent composition is D2: compound (2b) Liquid crystal aligning agent (S17B) with -a) = 35: 65 (weight ratio) and a polyamic acid concentration of 6.0% by weight was obtained.

[Reference Example 18B]
A solution containing polyamic acid (PA-7) was prepared in the same manner as in Reference Example 7B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of NMP and γ-butyl lactone (D3) as the first solvent and the compound (2b-a) as the specific solvent (B), and the solvent composition is NMP: D3: compound (2b-a) ) = 30:30:40 (weight ratio), a liquid crystal aligning agent (S18B) having a polyamic acid concentration of 6.0% by weight was obtained.
[Reference Example 19B]
A solution containing a polyamic acid intermediate (PA-8) was prepared in the same manner as in Reference Example 8B. This solution was poured into a large amount of methanol, and the obtained white precipitate was separated by filtration and dried to obtain a polyamic acid powder. This powder is dissolved in a mixed solvent of NMP and 3-butoxy-N, N-dimethylpropionamide (D2) as a first solvent and the compound (2b-b) as a specific solvent (B), and the solvent composition is NMP: D2: Compound (2b-b) = 30:30:40 (weight ratio), a liquid crystal aligning agent (S19B) having a polyamic acid concentration of 6.0% by weight was obtained.
[Reference Example 20B]
A powder of polyimide (PI-1) was obtained in the same manner as in Reference Example 9B. This powder is dissolved in a mixed solvent of 3-methoxy-N, N-dimethylpropionamide (D1) as a first solvent and compound (2b-a) as a specific solvent (B), and the solvent composition is D1: compound (2b) Liquid crystal aligning agent (S20B) of -a) = 50:50 (weight ratio) and solid content concentration 6.0 weight% was obtained.

<Evaluation of storage stability>
About each liquid crystal aligning agent obtained above, after filtering with a 1.0 micrometer filter, after storing for 1 month at -30 degreeC, it returns to room temperature (25 degreeC), and the presence or absence of the precipitate in a liquid crystal aligning agent is I observed it. The results are shown in Tables 3 and 4 below. In Tables 3 and 4, the case where no precipitate was observed in the liquid crystal aligning agent was shown as “○”, and the case where a precipitate was observed was shown as “x”.

<Evaluation of printability>
About each liquid crystal aligning agent prepared above, after filtering with a 1.0 micrometer filter, after storing for 6 months at -15 degreeC, it returned to room temperature (25 degreeC). Subsequently, the liquid crystal aligning agent was apply | coated to the transparent electrode surface of the glass substrate with a transparent electrode which consists of ITO films using liquid crystal aligning film printing machine (made by Nippon Photo Printing Co., Ltd. product). Thereafter, the solvent is removed by heating (pre-baking) on a hot plate at 80 ° C. for 1 minute, and then heating (post-baking) on a hot plate at 200 ° C. for 10 minutes to obtain a coating It formed. The coated film was observed with a microscope with a magnification of 20 times to examine the presence or absence of printing unevenness and pinholes. The evaluation was carried out with good printability (○) when print unevenness and pinholes were hardly observed as poor printability (×) when at least one of print unevenness and pinholes was observed. The results are shown in Tables 3 and 4 below.

The abbreviations in Tables 3 and 4 are as follows.
(Acid dianhydride)
AN-1; 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride AN-2; 2,3,5-tricarboxycyclopentylacetic acid dianhydride AN-3; pyromellitic acid dianhydride AN-4; Bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid 2: 4,6: 8-dianhydride (diamine)
DA-1: 1,5-bis (4-aminophenoxy) pentane DA-2: 2,4-diamino-N, N-diallylaniline DA-3: cholestanyl 3,5-diaminobenzoate 35DAB: 3,5- Diaminobenzoic acid (monoamine)
MA-1: n-dodecylamine (first solvent)
D1: 3-methoxy-N, N-dimethylpropionamide D2: 3-butoxy-N, N-dimethylpropionamide D3: γ-butyl lactone (second solvent)
D4: ethylene glycol dimethyl ether DEDG: diethylene glycol diethyl ether BC: butyl cellosolve (additive)
3-AMP: 3-aminomethylpyridine (compound represented by the above formula (c-1-16))
E1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

<Manufacture and evaluation of light alignment FFS liquid crystal display device>
(1) Production of FFS-Type Liquid Crystal Display Device Using Photoalignment Method An FFS-type liquid crystal display device 10 shown in FIG. 1 was produced. First, a glass substrate 11a having an electrode pair on one side of which is formed a bottom electrode 15 not having a pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb shape in this order The liquid crystal aligning agent (S1B) obtained above is used as an ink jet coating method on the surface of the glass substrate 11a having the transparent electrode and the one surface of the opposite glass substrate 11b, using the opposite glass substrate 11b not provided with A coating was formed. In addition, about a liquid crystal aligning agent (S1B), before apply | coating on a board | substrate, a solvent composition is prepared so that a viscosity may be set to 18 cP, as "NMP: (2b-a) = 60: 40 (weight ratio)." The liquid crystal aligning agent whose viscosity was adjusted was apply | coated on the board | substrate.
Next, this coated film is prebaked on a hot plate at 80 ° C. for 1 minute, and then heated (post bake) at 230 ° C. for 15 minutes in a nitrogen-replaced oven for about 1,000 Å A coating was formed. A schematic plan view of the top electrode 13 used here is shown in FIG. 2 (a) is a top view of the top electrode 13, and FIG. 2 (b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2 (a). In this reference example, a substrate having a top electrode in which the line width d1 of the electrodes is 4 μm and the distance d2 between the electrodes is 6 μm was used. In addition, as the top electrode 13, four drive electrodes of an electrode A, an electrode B, an electrode C, and an electrode D were used. The structure of the drive electrode of this liquid crystal display element is shown in FIG. In this case, the bottom electrode 15 functions as a common electrode acting on all of the four drive electrodes, and each of the four drive electrode regions is a pixel region.

Next, each surface of the coating film is irradiated with polarized ultraviolet light 300 J / m ² including a bright line of 313 nm from the substrate normal direction using an Hg-Xe lamp and a Glan-Taylor prism, respectively, and a pair having a liquid crystal alignment film I got the substrate. At this time, the direction of irradiation of polarized ultraviolet light is from the normal direction of the substrate, and the direction of polarization plane is set so that the direction of the line segment of the polarization plane of polarized ultraviolet light projected onto the substrate is the direction of double-headed arrow in FIG. The light irradiation process was performed.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied by screen printing to the outer periphery of the surface having the liquid crystal alignment film of one of the substrates described above, and then the liquid crystal alignment film surfaces of the pair of substrates are It was made to face each other, superimposed so that the direction of polarization plane of polarized ultraviolet light projected onto the substrate was parallel, and pressed, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, liquid crystal injection port was filled with liquid crystal “MLC-6221” manufactured by Merck from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, this was heated to 150 ° C. and then gradually cooled to room temperature in order to remove the flow alignment at the time of liquid crystal injection.
Next, polarizing plates were attached to both outer sides of the substrate to produce an FFS liquid crystal display element. At this time, one of the polarizing plates is attached so that the polarization direction is parallel to the projection direction of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film on the substrate surface, and the other has its polarization direction first. It stuck so as to be orthogonal to the polarization direction of the polarizing plate.
The above method is repeated to manufacture a total of five FFS liquid crystal display elements, one for evaluation of liquid crystal alignment, evaluation of voltage holding ratio, evaluation of heat resistance, bezel unevenness resistance, and evaluation of afterimage characteristics as described below. Provided. However, in all cases, ultraviolet irradiation was not performed under voltage application.

(2) Evaluation of Liquid Crystal Alignment With the FFS liquid crystal display device manufactured above, the presence or absence of abnormal domain in the change of light and dark when the voltage of 5 V is turned ON / OFF (applied / canceled) is observed with a magnification of 50 times did. In the evaluation, the case where no abnormal domain was observed was regarded as “good” in liquid crystal alignment, and the case where an abnormal domain was observed was regarded as “defective” in liquid crystal alignment. In this liquid crystal display element, the liquid crystal alignment was "good".
(3) Evaluation of voltage holding ratio After applying a voltage of 5 V at a temperature of 23 ° C. for 60 microseconds and a span of 167 milliseconds for the FFS type liquid crystal display device manufactured above, 167 milliseconds after release of application. The voltage holding ratio (VHR) was measured to be 99.4%. In addition, as a measuring apparatus, Toyo Co., Ltd. make and VHR-1 were used.
(4) Evaluation of heat resistance The voltage holding ratio was measured in the same manner as the evaluation of the above (3) voltage holding ratio, and the value was used as the initial VHR (VHR _BF ). Then, the liquid crystal display element after the initial VHR measurement was allowed to stand in an oven at 100 ° C. for 500 hours. Thereafter, the liquid crystal display element was allowed to stand at room temperature and allowed to cool to room temperature, and then the voltage retention was measured in the same manner as described above, and the value was taken as VHR _AF . Moreover, the change rate ((DELTA) VHR (%)) of the voltage retention before and behind provision of heat stress was calculated | required by the following numerical formula (EX-2).
V VHR (%) = ((VHR _BF- VHR _AF ) ÷ VHR _BF ) × 100 ... (EX-2)
The heat resistance is evaluated as heat resistance “good” when change rate ΔVHR is less than 4%, heat resistance “good” when it is 4% or more and less than 5%, heat resistance when it is 5% or more It went as sex "defective". As a result, ΔVHR was 2.9%, and the heat resistance of this liquid crystal display element was “good”.

(5) Non-uniformity resistance around bezel (bezel unevenness resistance)
The FFS-type liquid crystal display device manufactured above was stored for 30 days under conditions of 25 ° C. and 50% RH, and then was driven at an alternating voltage of 5 V to observe the lighting state. The evaluation is "excellent" if no luminance difference (more black or more white) is visually recognized around the sealing agent, but it is recognized if the luminance difference disappears within 5 minutes after lighting, "good", 5 minutes If the difference in brightness disappears within 20 minutes, the case where the difference in brightness is visible even after 20 minutes is regarded as "defective". As a result, in this liquid crystal display element, a luminance difference was not visually recognized around the sealing agent, and it was judged as "excellent".
(6) Evaluation of afterimage characteristics (DC afterimage evaluation)
The photoalignment type liquid crystal display device manufactured above was placed under an environment of 25 ° C. and 1 atm. The potential of the bottom electrode was set to a 0 V potential (ground potential), with the bottom electrode as a common electrode for all the four drive electrodes. The electrode B and the electrode D were short-circuited with the common electrode to apply 0 V, and a combined voltage of 3.5 V AC and 1 V DC was applied to the electrodes A and C for 2 hours. After 2 hours, a voltage of AC 1.5 V was immediately applied to all of the electrodes A to D. Then, from the time when a voltage of 1.5 V AC is started to be applied to all the drive electrodes, the drive stress application area (pixel area of the electrodes A and C) and the drive stress non-application area (pixel areas of the electrodes B and D) The time until the difference in brightness between the two and can not be visually confirmed was measured, and this was taken as the residual image elimination time. Note that, as this time is shorter, it is more difficult to cause an afterimage. The case where the residual image erasing time was less than 30 seconds was evaluated as “good”, the case where it was 30 seconds or more and less than 120 seconds as “good”, and the case where it was 120 seconds or more as “defective”. The residual image erasing time of the liquid crystal display element of 1 was 1 second, and the residual image characteristic was evaluated as "good".

As shown in Tables 3 and 4, all of the liquid crystal aligning agents of the reference examples using the specific solvent (B) have good storage stability when stored at low temperature, and also printability after low temperature storage It was good. On the other hand, the liquid crystal aligning agent of the reference comparative example was inferior in the storage stability and the printability after low temperature storage. From this, it was found that, by using the specific solvent (B), the storage stability can be improved while securing the coating property on the substrate.
[Example]

<Synthesis of Polyimide>
Synthesis Example 1: Synthesis of Polyimide (PI-1C)
22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride (TCA) as tetracarboxylic acid dianhydride, 8.6 g (0.08 mol) of p-phenylenediamine (PDA) as diamine ) And 10.5 g (0.02 mol) of cholestanyl 3,5-diaminobenzoate (HCDA) dissolved in 166 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C. for 6 hours to obtain a polyamic acid To give a solution containing 20% by weight. A small amount of the resulting polyamic acid solution was taken, N-methyl-2-pyrrolidone was added, and the solution viscosity was measured as a 10% by weight polyamic acid solution, and the solution viscosity was 90 mPa · s.

  Subsequently, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours . After dehydration ring closure reaction, the solvent in the system is solvent-substituted with fresh NMP (pyridine and acetic anhydride used for dehydration ring closure reaction are removed out of the system by this operation. The same applies hereinafter), and the imidization rate is about 68. A solution containing 26% by weight of polyimide (PI-1C) was obtained. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 45 mPa · s.

Synthesis Example 2: Synthesis of Polyimide (PI-2C)
22.5 g (0.1 mol) of TCA as tetracarboxylic dianhydride, 7.6 g (0.07 mol) of PDA as diamine, 5.2 g (0.01 mol) of HCDA and 4,4'-diaminodiphenylmethane (DDM) 4 0 g (0.02 mol) was dissolved in NMP 157 g and reacted at 60 ° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid. A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity was measured as a 10% by weight polyamic acid solution, and the solution viscosity was 110 mPa · s.

  Subsequently, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 16.6 g of pyridine and 21.4 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours . After dehydration ring closure reaction, the solvent in the system was replaced with fresh NMP to obtain a solution containing 26% by weight of polyimide (PI-2C) having an imidization rate of about 82%. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 62 mPa · s.

Synthesis Example 3: Synthesis of Polyimide (PI-3C)
2,4.9 g (0.10 mol) of 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride (BODA) as tetracarboxylic acid dianhydride 8.6 g (0.08 mol) of PDA as a diamine and 10.4 g (0.02 mol) of HCDA were dissolved in 176 g of NMP and reacted at 60 ° C. for 6 hours to obtain a solution containing 20% by weight of polyamic acid . A small amount of the obtained polyamic acid solution was fractionated, NMP was added, and the solution viscosity measured as a solution of 10 wt% polyamic acid concentration was 103 mPa · s.

  Subsequently, NMP was added to the obtained polyamic acid solution to make a solution having a polyamic acid concentration of 7% by weight, 11.9 g of pyridine and 15.3 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours . After dehydration ring closure reaction, the solvent in the system was replaced with fresh NMP to obtain a solution containing 26% by weight of polyimide (PI-3C) having an imidization rate of about 71%. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 57 mPa · s.

<Preparation of Liquid Crystal Alignment Agent>
[Example 1C]
In a solution containing 100 parts by weight of the synthesized polyimide (PI-1C), NMP, ethylene glycol mono-n-butyl ether (butyl cellosolve, BC) and a compound represented by the following formula (b1-1) (hereinafter referred to as “solvent” Compound (b1-1) ”was added, and the solvent composition was NMP: BC: Compound (b1-1) = 30: 50: 20 (weight ratio) to give a solution having a solid content concentration of 6.5% by weight. The solution was filtered using a filter with a pore size of 1 μm to prepare a liquid crystal aligning agent (S-1).

[Examples 2C to 18C, Comparative Examples 1C to 4C]
Liquid crystal aligning agents (S-2) to (S-18) and (SR-1) to (S-2) and (S-1) to (S-1), respectively, by the same method as in Example 1C except that the polyimide used and the solvent composition are changed as described in Table 5 (SR-4) was prepared respectively.

<Evaluation of printability>
Each of the liquid crystal aligning agents prepared above was evaluated for printability. Evaluation was performed as follows. First, for each of the prepared liquid crystal aligning agents, the amount of the liquid crystal aligning agent dropped onto the anilox roll using a liquid crystal alignment film printing machine (manufactured by Nippon Photographic Printer Co., Ltd., Ongstromer type “S40L-532”) The solution was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film under the condition of 20 drops of reciprocation (about 0.2 g). The application to the substrate was carried out 20 times using fresh substrate at 1 minute intervals.
Subsequently, the liquid crystal aligning agent was dispensed (one-way) on the anilox roll at intervals of one minute, and each time, an operation (hereinafter referred to as idle operation) for contacting the anilox roll and the printing plate was performed ten times in total Do not print on glass substrate). The idle operation is not performed in the normal manufacturing process of the liquid crystal display device, but is an operation performed to intentionally print the liquid crystal aligning agent on the substrate under severe conditions.

After ten idle operations, main printing was performed using a glass substrate. In this printing, after idle operation, five substrates are loaded at intervals of 30 seconds, and each substrate coated with the liquid crystal aligning agent is heated (prebaked) at 80 ° C. for 1 minute to remove the solvent, and then at 200 ° C. The film was heated (post-baked) for 10 minutes to form a coating having a film thickness of about 80 nm. Printability was evaluated by observing the pattern edge part (peripheral part of a printing pattern) of this coating film with a microscope with a magnification of 20 times. The evaluation was excellent (O) when no precipitate (considered to be a polyimide) was observed from the first printing after idle operation, while the precipitate was observed at the first printing after idle operation, The case where precipitates disappeared during 5 times of printing was regarded as good (Δ), and the case where precipitates were observed even after repeating the main printing 5 times was regarded as defective (×). The evaluation results are shown in Table 5 below. In the liquid crystal aligning agent having good printability, it has been experimentally found that the precipitates are improved (disappeared) while the substrate is continuously introduced.
Moreover, the printability of the liquid crystal aligning agent was evaluated by performing operation similar to the above except having changed the frequency | count of idle operation into 15 times, 20 times, and 25 times, respectively. The evaluation results are shown in Table 5 below.

<Evaluation of drying level of membrane surface>
The drying level of the film surface was evaluated for the coating film after the prebaking in the above-mentioned "evaluation of printability". The evaluation was made as good (○) when no sticky feeling remained when touching the film surface with a hand, and as poor (×) when sticky feeling remained. The evaluation results are shown in Table 5 below. In addition, it evaluated using the board | substrate of this printing implemented after idle operation of 10 times here.

In addition, the symbol of the solvent composition in Table 5 has the following meaning, respectively.
a: N-methyl-2-pyrrolidone (NMP)
b: ethylene glycol mono-n-butyl ether (BC)
d: compound (b1-1)
e: compound represented by the following formula (b2-1) f: compound represented by the following formula (b2-2) g: N-vinyl-2-pyrrolidone h: N-cyclohexyl-2-pyrrolidone i: N-octyl-2-pyrrolidone

  With regard to the printability, no precipitate was observed in the liquid crystal alignment agents of the examples from the first printing after the 10 idle rotations. This was the same even after 15 idle operations. In addition, when the number of idle operation was increased to 20 times and 25 times, some precipitates were observed at the first printing, but the precipitates were observed until five main printings were completed. It has disappeared. From these facts, it was found that the liquid crystal aligning agent of the example was less likely to generate precipitates during printing, and the printability was good.

  DESCRIPTION OF SYMBOLS 10 ... Liquid crystal display element, 11a, 11b ... Glass substrate, 12 ... Liquid crystal aligning film, 13 ... Top electrode, 14 ... Insulating layer, 15 ... Bottom electrode, 16 ... Liquid crystal layer

Claims (9)

A composition comprising at least one polymer (A) selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and a solvent,
A composition, wherein the solvent contains at least one selected from the group consisting of a compound represented by the following formula (b1) and a compound represented by the following formula (b2).

(In formula (b1), R is an alkyl group having 1 to 3 carbon atoms, and n is an integer of 0 to 2. In the formula (b2), m is an integer of 0 to 2). It is a liquid crystal aligning agent containing at least one polymer (A) selected from the group consisting of polyamic acid, polyimide and polyamic acid ester, and a solvent,
A liquid crystal aligning agent, wherein the solvent contains at least one selected from the group consisting of a compound represented by the following formula (b1) and a compound represented by the following formula (b2).

(In formula (b1), R is an alkyl group having 1 to 3 carbon atoms, and n is an integer of 0 to 2. In the formula (b2), m is an integer of 0 to 2). The polymer (A) contains a polymer having a partial structure derived from at least one diamine selected from the group consisting of compounds represented by the following formulas (d-1) to (d-5) The liquid crystal aligning agent of Claim 2.

(In formula (d-1), X ¹ and X ² are each independently a single bond, -O-, -S-, -OCO- or -COO-, and Y ¹ is an oxygen atom or a sulfur atom R ¹¹ and R ¹² are each independently an alkanediyl group having 1 to 3 carbon atoms, R ⁸ and R ⁹ are each independently a hydrogen atom or a protecting group, n 1 is 0 or 1 N2 and n3 are integers satisfying n2 + n3 = 2 when n1 = 0, and n2 = n3 = 1 when n1 = 1, and in the formula (d-2), X ³ is a single integer. Is a bond, -O- or -S-, m1 is an integer of 0 to 3. m2 is an integer of 1 to 12 when m1 = 0, and m2 if m1 is an integer of 1 to 3 In the formula (d-3), R ³ is a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ⁴ is a hydrogen atom or carbon R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and in the formula (d-4), X ⁴ and X ⁵ are each independently And a single bond, -O-, -COO- or -OCO-, R ⁷ is an alkanediyl group having 1 to 3 carbon atoms, and A ⁴ is a single bond or an alkanediyl having 1 to 3 carbon atoms A is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, k is 0 or 1, provided that a and b are simultaneously 0. never in formula ^{(d-5), a} 5 represents a single bond, alkanediyl group or a fluoroalkyl alkanediyl group having 1 to 6 carbon atoms having 1 to 12 carbon atoms, ^{a 6} is -O -., - COO -, - OCO -, - NHCO -, - CONH- or -CO- indicates a monovalent organic ^{a 7} is having a steroid skeleton Are shown.)   The content of at least one compound selected from the group consisting of a compound represented by the above formula (b1) and a compound represented by the following formula (b2) is 1 to 70% by weight of the total amount of the solvent The liquid crystal aligning agent of Claim 2 or 3. The polymer (A) is a compound represented by the following formula (t-1), 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride The liquid crystal aligning agent according to any one of claims 2 to 4, which is a polymer having a partial structure derived from at least one tetracarboxylic acid dianhydride selected from the group consisting of and pyromellitic dianhydride. .

(In formula (t-1), X ⁷ , X ⁸ , X ⁹ and X ¹⁰ are each independently a single bond or a methylene group, and j is an integer of 1 to 3).   An amine compound having one primary amino group in the molecule and a nitrogen-containing aromatic heterocycle, and the primary amino group being bonded to a chain hydrocarbon group or an alicyclic hydrocarbon group (C The liquid crystal aligning agent as described in any one of Claims 2-5 which further contain. The liquid crystal aligning agent of Claim 6 whose said amine compound (C) is a compound represented by following formula (c-1).

(In Formula (c-1), A ¹ is a divalent organic group having a chain hydrocarbon group or an alicyclic hydrocarbon group, and A ² is a nitrogen-containing aromatic heterocycle. The primary amino group in the formula is bonded to the chain hydrocarbon group or alicyclic hydrocarbon group that A ¹ has.)   The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 2-7.   The liquid crystal display element which comprises the liquid crystal aligning film of Claim 8.

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